Production & Supply Chain
Boosting Photocatalytic Hydrogen Production from Water by Photothermally Induced Biphase Systems
Feb 2021
Publication
Solar-driven hydrogen production from water using particulate photocatalysts is considered the most economical and effective approach to produce hydrogen fuel with little environmental concern. However the efficiency of hydrogen production from water in particulate photocatalysis systems is still low. Here we propose an efficient biphase photocatalytic system composed of integrated photothermal–photocatalytic materials that use charred wood substrates to convert liquid water to water steam simultaneously splitting hydrogen under light illumination without additional energy. The photothermal–photocatalytic system exhibits biphase interfaces of photothermally-generated steam/photocatalyst/hydrogen which significantly reduce the interface barrier and drastically lower the transport resistance of the hydrogen gas by nearly two orders of magnitude. In this work an impressive hydrogen production rate up to 220.74 μmol h−1 cm−2 in the particulate photocatalytic systems has been achieved based on the wood/CoO system demonstrating that the photothermal–photocatalytic biphase system is cost-effective and greatly advantageous for practical applications.
Hydrogen‐Rich Gas Production from Two‐Stage Catalytic Pyrolysis of Pine Sawdust with Calcined Dolomite
Jan 2022
Publication
Tao Xu,
Jue Xu and
Yongping Wu
The potential of catalytic pyrolysis of biomass for hydrogen and bio‐oil production has drawn great attention due to the concern of clean energy utilization and decarbonization. In this paper the catalytic pyrolysis of pine sawdust with calcined dolomite was carried out in a novel moving bed reactor with a two‐stage screw feeder. The effects of pyrolysis temperature (700–900 °C) and catalytic temperature (500–800 °C) on pyrolysis performance were investigated in product distribution gas composition and gas properties. The results showed that with the temperature increased pyrolysis gas yield in‐ creased but the yield of solid and liquid products decreased. With the increase in temperature the CO and H2 content increased significantly while the CO2 and CH4 decreased correspondingly. The calcined dolomite can remove the tar by 44% and increased syngas yield by 52.9%. With the increasing catalytic temperature the catalytic effect of calcined dolomite was also enhanced.
Pathways to Low-cost Clean Hydrogen Production with Gas Switching Reforming
Feb 2020
Publication
Gas switching reforming (GSR) is a promising technology for natural gas reforming with inherent CO2 capture. Like conventional steam methane reforming (SMR) GSR can be integrated with CO2 -gas shift and pressure swing adsorption units for pure hydrogen production. The resulting GSR-H2 process concept was techno-economically assessed in this study. Results showed that GSR-H2 can achieve 96% CO2 capture at a CO2 avoidance cost of 15 $/ton (including CO2 transport and storage). Most components of the GSR-H2 process are proven technologies but long-term oxygen carrier stability presents an important technical uncertainty that can adversely affect competitiveness when the material lifetime drops below one year. Relative to the SMR benchmark GSR-H2 replaces some fuel consumption with electricity consumption making it more suitable to regions with higher natural gas prices and lower electricity prices. Some minor alterations to the process configuration can adjust the balance between fuel and electricity consumption to match local market conditions. The most attractive commercialization pathway for the GSR-H2 technology is initial construction without CO2 capture followed by simple retrofitting for CO2 capture when CO2 taxes rise and CO2 transport and storage infrastructure becomes available. These features make the GSR-H2 technology robust to almost any future energy market scenario.
Secure, Affordable, Low Carbon: Gas in our Future Energy System
Feb 2020
Publication
Our gas network is one of the best developed in the world providing safe secure affordable energy to homes and businesses across the UK.<br/><br/>To meet the biggest energy challenge of our generation – making deep cuts to carbon emissions by 2050 – it needs to embrace new technology which builds on these strengths and delivers the integrated flexible network of the future. This briefing sets out how it is already doing that. Take a look at our Gas Futures Messages booklet attached.
Sustainable Hydrogen Production: A Role for Fusion
Apr 2007
Publication
This Meeting Report summarises the findings of a two-day workshop in April 2007 at the Culham Science Centre and Worcester College Oxford which explored the potential for large-scale Hydrogen production through methods other than electrolysis.<br/>Operating at the cusp of research and policy-making the UK Energy Research Centre's mission is to be the UK's pre-eminent centre of research and source of authoritative information and leadership on sustainable energy systems. The Centre takes a whole systems approach to energy research incorporating economics engineering and the physical environmental and social sciences while developing and maintaining the means to enable cohesive research in energy. A key supporting function of UKERC is the Meeting Place based in Oxford which aims to bring together members of the UK energy community and overseas experts from different disciplines to learn identify problems develop solutions and further the energy debate.
Charge Carrier Mapping for Z-scheme Photocatalytic Water-splitting Sheet via Categorization of Microscopic Time-resolved Image Sequences
Jun 2021
Publication
Photocatalytic water splitting system using particulate semiconductor materials is a promising strategy for converting solar energy into hydrogen and oxygen. In particular visible-light-driven ‘Z-scheme’ printable photocatalyst sheets are cost-effective and scalable. However little is known about the fundamental photophysical processes which are key to explaining and promoting the photoactivity. Here we applied the pattern-illumination time-resolved phase microscopy for a photocatalyst sheet composed of Mo-doped BiVO4 and Rh-doped SrTiO3 with indium tin oxide as the electron mediator to investigate photo-generated charge carrier dynamics. Using this method we successfully observed the position- and structure-dependent charge carrier behavior and visualized the active/inactive sites in the sheets under the light irradiation via the time sequence images and the clustering analysis. This combination methodology could provide the material/synthesis optimization methods for the maximum performance of the photocatalyst sheets.
Hydrogen Production from Natural Gas and Biomethane with Carbon Capture and Storage – A Techno-environmental Analysis
Mar 2020
Publication
This study presents an integrated techno-environmental assessment of hydrogen production from natural gas and biomethane combined with CO2 capture and storage (CCS). We have included steam methane reforming (SMR) and autothermal reforming (ATR) for syngas production. CO2 is captured from the syngas with a novel vacuum pressure swing adsorption (VPSA) process that combines hydrogen purification and CO2 separation in one cycle. As comparison we have included cases with conventional amine-based technology. We have extended standard attributional Life Cycle Assessment (LCA) following ISO standards with a detailed carbon balance of the biogas production process (via digestion) and its by-products. The results show that the life-cycle greenhouse gas (GHG) performance of the VPSA and amine-based CO2 capture technologies is very similar as a result of comparable energy consumption. The configuration with the highest plant-wide CO2 capture rate (almost 100% of produced CO2 captured) is autothermal reforming with a two-stage water-gas shift and VPSA CO2 capture – because the latter has an inherently high CO2 capture rate of 98% or more for the investigated syngas. Depending on the configuration the addition of CCS to natural gas reforming-based hydrogen production reduces its life-cycle Global Warming Potential by 45–85 percent while the other environmental life-cycle impacts slightly increase. This brings natural gas-based hydrogen on par with renewable electricity-based hydrogen regarding impacts on climate change. When biomethane is used instead of natural gas our study shows potential for net negative greenhouse gas emissions i.e. the net removal of CO2 over the life cycle of biowaste-based hydrogen production. In the special case where the biogas digestate is used as agricultural fertiliser and where a substantial amount of the carbon in the digestate remains in the soil the biowaste-based hydrogen reaches net-negative life cycle greenhouse gas emissions even without the application of CCS. Addition of CCS to biomethane-based hydrogen production leads to net-negative emissions in all investigated cases.
Pd Catalysts Supported on Bamboo-Like Nitrogen-Doped Carbon Nanotubes for Hydrogen Production
Mar 2021
Publication
Bamboo-like nitrogen-doped carbon nanotubes (N-CNTs) were used to synthesize supported palladium catalysts (0.2–2 wt.%) for hydrogen production via gas phase formic acid decomposition. The beneficial role of nitrogen centers of N-CNTs in the formation of active isolated palladium ions and dispersed palladium nanoparticles was demonstrated. It was shown that although the surface layers of N-CNTs are enriched with graphitic nitrogen palladium first interacts with accessible pyridinic centers of N-CNTs to form stable isolated palladium ions. The activity of Pd/N-CNTs catalysts is determined by the ionic capacity of N-CNTs and dispersion of metallic nanoparticles stabilized on the nitrogen centers. The maximum activity was observed for the 0.2% Pd/N-CNTs catalyst consisting of isolated palladium ions. A ten-fold increase in the concentration of supported palladium increased the contribution of metallic nanoparticles with a mean size of 1.3 nm and decreased the reaction rate by only a factor of 1.4.
Design of Experiment to Predict the Time Between Hydrogen Purges for an Air-breathing PEM Fuel Cell in Dead-end Mode in a Closed Environment
Feb 2021
Publication
Fuel cells are promising technologies for zero-emission energy conversion. They are used in several applications such as power plants cars and even submarines. Hydrogen supply is crucial for such systems and using Proton Exchange Membrane Fuel Cell in dead-end mode is a solution to save hydrogen. Since water and impurities accumulate inside the stack purging is necessary. However the importance of operating parameters is not well known for fuel cells working in closed environments. A Design of Experiment approach studying time between two purges and cell performance was conducted on an air-breathing stack in a closed environment. The most influential parameters on the time between two purges are the relative humidity and the current load. Convection in the closed environment can decrease the stability of the fuel cell. A linear model with interactions between these last three parameters was found to accurately describe the studied responses.
Study on Hydrogen from Renewable Resources in the EU
Feb 2016
Publication
Hydrogen can be produced from a broad range of renewable energy sources acting as a unique energy hub providing low or zero emission energy to all energy consuming sectors. Technically and efficiently producing hydrogen from renewable sources is a key enabler for these developments.<br/>Traditionally hydrogen has been produced from fossil sources by steam methane reforming of natural gas. At present the technology of choice to produce renewable ‘green’ hydrogen is water electrolysis using renewable electricity. The FCH JU has been supporting research and development of electrolyser technology and application projects aiming to increase the energy efficiency of electrolytic hydrogen production from renewable sources and to reduce costs.<br/>This study complements these activities by focusing on renewable hydrogen generation other than electrolysis. In this report these alternative hydrogen generation technologies are described characterized by their technical capabilities maturity and economic performance and assessed for their future potential.<br/>A methodology has been devised to first identify and structure a set of relevant green hydrogen pathways (eleven pathways depicted in the figure below) analyse them at a level of detail allowing a selection of those technologies which fit into and promise early commercialization in the framework of FCH 2 JU’s funding program.<br/>These originally proposed eleven pathways use solar thermal energy sunlight or biomass as major energy input.
Potential for Hydrogen Production from Sustainable Biomass with Carbon Capture and Storage
Jan 2022
Publication
Low-carbon hydrogen is an essential element in the transition to net-zero emissions by 2050. Hydrogen production from biomass is a promising bio-energy with carbon capture and storage (BECCS) scheme that could produce low-carbon hydrogen and generate the carbon dioxide removal (CDR) envisioned to be required to offset hard-to-abate emissions. Here we design a BECCS supply chain for hydrogen production from biomass with carbon capture and storage and quantify at high spatial resolution the technical potential for hydrogen production and CDR in Europe. We consider sustainable biomass feedstocks that have minimal impacts on food security and biodiversity namely agricultural residues and waste. We find that this BECCS supply chain can produce up to 12.5 Mtons of H2 per year (currently ~10 Mtons of H2 per year are used in Europe) and remove up to 133 Mtons CO2 per year from the atmosphere (or 3% of European total greenhouse gas emissions). We then perform a geospatial analysis to quantify transportation distances between where biomass feedstocks are located and potential hydrogen users and find that 20% of hydrogen potential is located within 25 km from hard-toelectrify industries. We conclude that BECCS supply chains for hydrogen production from biomass represent an overlooked near-term opportunity to generate carbon dioxide removal and low-carbon hydrogen.
Durability of Anion Exchange Membrane Water Electrolyzers
Apr 2021
Publication
Interest in the low-cost production of clean hydrogen is growing. Anion exchange membrane water electrolyzers (AEMWEs) are considered one of the most promising sustainable hydrogen production technologies because of their ability to split water using platinum group metal-free catalysts less expensive anode flow fields and bipolar plates. Critical to the realization of AEMWEs is understanding the durability-limiting factors that restrict the long-term use of these devices. This article presents both durability-limiting factors and mitigation strategies for AEMWEs under three operation modes i.e. pure water-fed (no liquid electrolyte) concentrated KOH-fed and 1 wt% K2CO3-fed operating at a differential pressure of 100 psi. We examine extended-term behaviors of AEMWEs at the single-cell level and connect their behavior with the electrochemical chemical and mechanical instability of single-cell components. Finally we discuss the pros and cons of AEMWEs under these operation modes and provide direction for long-lasting AEMWEs with highly efficient hydrogen production capabilities.
Future Cost and Performance of Water Electrolysis: An Expert Elicitation Study
Nov 2017
Publication
The need for energy storage to balance intermittent and inflexible electricity supply with demand is driving interest in conversion of renewable electricity via electrolysis into a storable gas. But high capital cost and uncertainty regarding future cost and performance improvements are barriers to investment in water electrolysis. Expert elicitations can support decision-making when data are sparse and their future development uncertain. Therefore this study presents expert views on future capital cost lifetime and efficiency for three electrolysis technologies: alkaline (AEC) proton exchange membrane (PEMEC) and solid oxide electrolysis cell (SOEC). Experts estimate that increased R&D funding can reduce capital costs by 0–24% while production scale-up alone has an impact of 17–30%. System lifetimes may converge at around 60000–90000 h and efficiency improvements will be negligible. In addition to innovations on the cell-level experts highlight improved production methods to automate manufacturing and produce higher quality components. Research into SOECs with lower electrode polarisation resistance or zero-gap AECs could undermine the projected dominance of PEMEC systems. This study thereby reduces barriers to investment in water electrolysis and shows how expert elicitations can help guide near-term investment policy and research efforts to support the development of electrolysis for low-carbon energy systems.
Synthesis and Characterisation of Platinum-cobalt-manganese Ternary Alloy Catalysts Supported on Carbon Nanofibers: An Alternative Catalyst for Hydrogen Evolution Reaction
Mar 2020
Publication
A systematic method for obtaining a novel electrode structure based on PtCoMn ternary alloy catalyst supported on graphitic carbon nanofibers (CNF) for hydrogen evolution reaction (HER) in acidic media is proposed. Ternary alloy nanoparticles (Co0.6Mn0.4 Pt) with a mean crystallite diameter under 10 nm were electrodeposited onto a graphitic support material using a two-step pulsed deposition technique. Initially a surface functionalisation of the carbon nanofibers is performed with the aid of oxygen plasma. Subsequently a short galvanostatic pulse electrodeposition technique is applied. It has been demonstrated that if pulsing current is employed compositionally controlled PtCoMn catalysts can be achieved. Variations of metal concentration ratios in the electrolyte and main deposition parameters such as current density and pulse shape led to electrodes with relevant catalytic activity towards HER. The samples were further characterised using several physico-chemical methods to reveal their morphology structure chemical and electrochemical properties. X-ray diffraction confirms the PtCoMn alloy formation on the graphitic support and energy dispersive X-ray spectroscopy highlights the presence of the three metallic components from the alloy structure. The preliminary tests regarding the electrocatalytic activity of the developed electrodes display promising results compared to commercial Pt/C catalysts. The PtCoMn/CNF electrode exhibits a decrease in hydrogen evolution overpotential of about 250 mV at 40 mA cm−2 in acidic solution (0.5 M H2SO4) when compared to similar platinum based electrodes (Pt/CNF) and a Tafel slope of around 120 mV dec−1 indicating that HER takes place under the Volmer-Heyrovsky mechanismm
Methodology for Efficient Parametrisation of Electrochemical PEMFC Model for Virtual Observers: Model Based Optimal Design of Experiments Supported by Parameter Sensitivity Analysis
Nov 2020
Publication
Determination of the optimal design of experiments that enables efficient parametrisation of fuel cell (FC) model with a minimum parametrisation data-set is one of the key prerequisites for minimizing costs and effort of the parametrisation procedure. To efficiently tackle this challenge the paper present an innovative methodology based on the electrochemical FC model parameter sensitivity analysis and application of D-optimal design plan. Relying on this consistent methodological basis the paper answers fundamental questions: a) on a minimum required data-set to optimally parametrise the FC model and b) on the impact of reduced space of operational points on identifiability of individual calibration parameters. Results reveal that application of D-optimal DoE enables enhancement of calibration parameters information resulting in up to order of magnitude lower relative standard errors on smaller data-sets. In addition it was shown that increased information and thus identifiability inherently leads to improved robustness of the FC electrochemical model.
Dual Z-scheme Charge Transfer in TiO2–Ag–Cu2O Composite for Enhanced Photocatalytic Hydrogen Generation
Apr 2015
Publication
Photocatalytic hydrogen generation is one of the most promising solutions to convert solar power into green chemical energy. In this work a multi-component TiO2–Ag–Cu2O composite was obtained through simple impregnation-calcination of Cu2O and subsequent photodeposition of Ag onto electrospun TiO2 nanotubes. The resulting TiO2–Ag–Cu2O photocatalyst exhibits excellent photocatalytic H2 evolution activity due to the synergetic effect of Ag and Cu2O on electrospun TiO2nanotubes. A dual Z-scheme charge transfer pathway for photocatalytic reactions over TiO2–Ag–Cu2O composite was proposed and discussed. This work provides a prototype for designing Z-scheme photocatalyst with Ag as an electron mediator.
Effect of Anion Exchange Ionomer Content on Electrode Performance in AEM Water Electrolysis
Aug 2020
Publication
Anion exchange membrane water electrolysis (AEMWE) has acquired substantial consideration as a cost-effective hydrogen production technology. The anion ionomer content in the catalyst layers during hydrogen and oxygen evolution reaction (HER and OER) is of ultimate significance. Herein an in-situ half-cell analysis with reference electrodes was carried out for simultaneous potential measurements and identification of the influence of the anion exchange ionomer (AEI) content on anode and cathode performance. The measured half-cell potentials proved the influence of AEI content on the catalytic activity of HER and OER which was supported by the rotating disk electrode (RDE) measurements. Cathode overpotential of Ni/C was not negligible and more affected by the AEI content than anode with the optimized AEI content of 10 wt% while NiO anode OER overpotential was independent of the AEI content. For the same AEI content PGM catalysts showed higher electroactivity than Ni-based catalysts for HER and OER and the cathode catalyst's intrinsic activity is of high importance in the AEM electrolysis operation. Post-mortem analysis by SEM mapping of both AEI and catalyst distributions on the electrode surface showed the effect of AEI loading on the catalyst morphology which could be related to the electrode performance.
A Comprehensive Review of Microbial Electrolysis Cells (MEC) Reactor Designs and Configurations for Sustainable Hydrogen Gas Production
Nov 2015
Publication
Hydrogen gas has tremendous potential as an environmentally acceptable energy carrier for vehicles. A cutting edge technology called a microbial electrolysis cell (MEC) can achieve sustainable and clean hydrogen production from a wide range of renewable biomass and wastewaters. Enhancing the hydrogen production rate and lowering the energy input are the main challenges of MEC technology. MEC reactor design is one of the crucial factors which directly influence on hydrogen and current production rate in MECs. The rector design is also a key factor to upscaling. Traditional MEC designs incorporated membranes but it was recently shown that membrane-free designs can lead to both high hydrogen recoveries and production rates. Since then multiple studies have developed reactors that operate without membranes. This review provides a brief overview of recent advances in research on scalable MEC reactor design and configurations.
Achievements of European Projects on Membrane Reactor for Hydrogen Production
May 2017
Publication
Membrane reactors for hydrogen production can increase both the hydrogen production efficiency at small scale and the electric efficiency in micro-cogeneration systems when coupled with Polymeric Electrolyte Membrane fuel cells. This paper discusses the achievements of three European projects (FERRET FluidCELL BIONICO) which investigate the application of the membrane reactor concept to hydrogen production and micro-cogeneration systems using both natural gas and biofuels (biogas and bio-ethanol) as feedstock. The membranes used to selectively separate hydrogen from the other reaction products (CH4 CO2 H2O etc.) are of asymmetric type with a thin layer of Pd alloy (<5 μm) and supported on a ceramic porous material to increase their mechanical stability. In FERRET the flexibility of the membrane reactor under diverse natural gas quality is validated. The reactor is integrated in a micro-CHP system and achieves a net electric efficiency of about 42% (8% points higher than the reference case). In FluidCELL the use of bio-ethanol as feedstock for micro-cogeneration Polymeric Electrolyte Membrane based system is investigated in off-grid applications and a net electric efficiency around 40% is obtained (6% higher than the reference case). Finally BIONICO investigates the hydrogen production from biogas. While BIONICO has just started FERRET and FluidCELL are in their third year and the two prototypes are close to be tested confirming the potentiality of membrane reactor technology at small scale.
A Perspective on Hydrogen Investment, Deployment and Cost Competitiveness
Feb 2021
Publication
Deployment and investments in hydrogen have accelerated rapidly in response to government commitments to deep decarbonisation establishing hydrogen as a key component in the energy transition.
To help guide regulators decision-makers and investors the Hydrogen Council collaborated with McKinsey & Company to release the report ‘Hydrogen Insights 2021: A Perspective on Hydrogen Investment Deployment and Cost Competitiveness’. The report offers a comprehensive perspective on market deployment around the world investment momentum as well as implications on cost competitiveness of hydrogen solutions.
The document can be downloaded from their website
To help guide regulators decision-makers and investors the Hydrogen Council collaborated with McKinsey & Company to release the report ‘Hydrogen Insights 2021: A Perspective on Hydrogen Investment Deployment and Cost Competitiveness’. The report offers a comprehensive perspective on market deployment around the world investment momentum as well as implications on cost competitiveness of hydrogen solutions.
The document can be downloaded from their website
Review of Renewable Energy-based Hydrogen Production Processes for Sustainable Energy Innovation
Dec 2019
Publication
In this review we primarily analyze the hydrogen production technologies based on water and biomass including the economic technological and environmental impacts of different types of hydrogen production technologies based on these materials and comprehensively compare them. Our analyses indicate that all renewable energy-based approaches for hydrogen production are more environmentally friendly than fossil-based hydrogen generation approaches. However the technical ease and economic efficiency of hydrogen production from renewable sources of energy needs to be further improved in order to be applied on a large scale. Compared with other renewable energy-based methods hydrogen production via biomass electrolysis has several advantages including the ease of directly using raw biomass. Furthermore its environmental impact is smaller than other approaches. Moreover using a noble metal catalyst-free anode for this approach can ensure a considerably low power consumption which makes it a promising candidate for clean and efficient hydrogen production in the future.
Towards an Understanding of Hydrogen Supply Chains: A Structured Literature Review Regarding Sustainability Evaluation
Oct 2021
Publication
Hydrogen technologies have received increased attention in research and development to foster the shift towards carbon-neutral energy systems. Depending on the specific production techniques transportation concepts and application areas hydrogen supply chains (HSCs) can be anything from part of the energy transition problem to part of the solution: Even more than battery-driven electric mobility hydrogen is a polyvalent technology and can be used in very different contexts with specific positive or negative sustainability impacts. Thus a detailed sustainability evaluation is crucial for decision making in the context of hydrogen technology and its diverse application fields. This article provides a comprehensive structured literature review in the context of HSCs along the triple bottom line dimensions of environmental economic and social sustainability analyzing a total of 288 research papers. As a result we identify research gaps mostly regarding social sustainability and the supply chain stages of hydrogen distribution and usage. We suggest further research to concentrate on these gaps thus strengthening our understanding of comprehensive sustainability evaluations for HSCs especially in social sustainability evaluation. In addition we provide an additional approach for discussion by adding literature review results from neighboring fields highlighting the joint challenges and insights regarding sustainability evaluation.
Modelling Decentralized Hydrogen Systems: Lessons Learned and Challenges from German Regions
Feb 2022
Publication
Green hydrogen produced by power‐to‐gas will play a major role in the defossilization of the energy system as it offers both carbon‐neutral chemical energy and the chance to provide flexibility. This paper provides an extensive analysis of hydrogen production in decentralized energy systems as well as possible operation modes (H2 generation or system flexibility). Modelling was realized for municipalities—the lowest administrative unit in Germany thus providing high spatial resolution—in the linear optimization framework OEMOF. The results allowed for a detailed regional analysis of the specific operating modes and were analyzed using full‐load hours share of used negative residual load installed capacity and levelized cost of hydrogen to derive the operation mode of power‐to‐gas to produce hydrogen. The results show that power‐to‐gas is mainly characterized by constant hydrogen production and rarely provides flexibility to the system. Main drivers of this dominant operation mode include future demand for hydrogen and the fact that high full‐load hours reduce hydrogen‐production costs. However changes in the regulatory market and technical framework could promote more flexibility and support possible use cases for the central technology to succeed in the energy transition.
Thoughts on the Prospects of Renewable Hydrogen
Oct 2020
Publication
In the last two years or so there has been increasing interest in hydrogen as an energy source in Australia and around the world. Notably this is not the first time that hydrogen has caught our collective interest. Most recently the 2000s saw a substantial investment in hydrogen research development and demonstration around the world. Prior to that the oil crises of the 1970s also stimulated significant investment in hydrogen and earlier still the literature on hydrogen was not lacking. And yet the hydrogen economy is still an idea only.<br/>So what if anything might be different this time?<br/>This is an important question that we all need to ask and for which the author can only give two potential answers. First our need to make dramatic reductions in greenhouse gas (GHG) emissions has become more pressing since these previous waves of interest. Second renewable energy is considerably more affordable now than it was before and it has consistently outperformed expectations in terms of cost reductions by even its strongest supporters.<br/>While this dramatic and ongoing reduction in the cost of renewables is very promising our need to achieve substantial GHG emission reductions is the crucial challenge. Moreover meeting this challenge needs to be achieved with as little adverse social and economic impact as possible.<br/>When considering what role hydrogen might play we should first think carefully about the massive scale and complexity of our global energy system and the typical prices of the major energy commodities. This provides insights into what opportunities hydrogen may have. Considering a temperate country with a small population like Australia we see that domestic natural gas and transport fuel markets are comparable to and even larger than the electricity market on an energy basis.
Techno-Economic Analysis of Hydrogen and Electricity Production by Biomass Calcium Looping Gasification
Feb 2022
Publication
Combined cycle biomass calcium looping gasification is proposed for a hydrogen and electricity production (CLGCC–H) system. The process simulation Aspen Plus is used to conduct techno-economic analysis of the CLGCC–H system. The appropriate detailed models are set up for the proposed system. Furthermore a dual fluidized bed is optimized for hydrogen production at 700 °C and 12 bar. For comparison calcium looping gasification with the combined cycle for electricity (CLGCC) is selected with the same parameters. The system exergy and energy efficiency of CLGCC–H reached as high as 60.79% and 64.75% while the CLGCC system had 51.22% and 54.19%. The IRR and payback period of the CLGCC–H system based on economic data are calculated as 17.43% and 7.35 years respectively. However the CLGCC system has an IRR of 11.45% and a payback period of 9.99 years respectively. The results show that the calcium looping gasification-based hydrogen and electricity coproduction system has a promising market prospect in the near future.
Fabrication of CdS/β-SiC/TiO2 Tri-composites That Exploit Hole- and Electron-transfer Processes for Photocatalytic Hydrogen Production Under Visible Light
Dec 2017
Publication
In this work CdS/SiC/TiO2 tri-composite photocatalysts that exploit electron- and hole-transfer processes were fabricated using an easy two-step method in the liquid phase. The photocatalyst with a 1:1:1 M ratio of CdS/SiC/TiO2 exhibited a rate of hydrogen evolution from an aqueous solution of sodium sulfite and sodium sulfide under visible light of 137 μmol h−1 g−1 which is 9.5 times that of pure CdS. β-SiC can act as a sink for the photogenerated holes because the valence band level of β-SiC is higher than the corresponding bands in CdS and TiO2. In addition the level of the conduction band of TiO2 is lower than those of CdS and β-SiC so TiO2 can act as the acceptor of the photogenerated electrons. Our results demonstrate that hole transfer and absorption in the visible light region lead to an effective hydrogen-production scheme.
Methane Pyrolysis in a Molten Gallium Bubble Column Reactor for Sustainable Hydrogen Production: Proof of Concept & Techno-economic Assessment
Dec 2020
Publication
Nowadays nearly 50% of the hydrogen produced worldwide comes from Steam Methane Reforming (SMR) at an environmental burden of 10.5 tCO2 eq/tH2 accelerating the consequences of global warming. One way to produce clean hydrogen is via methane pyrolysis using melts of metals and salts. Compared to SMR significant less CO2 is produced due to conversion of methane into hydrogen and carbon making this route more sustainable to generate hydrogen. Hydrogen is produced with high purity and solid carbon is segregated and deposited on the molten bath. Carbon may be sold as valuable co-product making industrial scale promising. In this work methane pyrolysis was performed in a quartz bubble column using molten gallium as heat transfer agent and catalyst. A maximum conversion of 91% was achieved at 1119 °C and ambient pressure with a residence time of the bubbles in the liquid of 0.5 s. Based on in-depth analysis of the carbon it can be characterized as carbon black. Techno-economic and sensitivity analyses of the industrial concept were done for different scenarios. The results showed that if co-product carbon is saleable and a CO2 tax of 50 euro per tonne is imposed to the processes the molten metal technology can be competitive with SMR.
MELCOR Analysis of a SPARC Experiment for Spray-PAR Interaction During a Hydrogen Release
Oct 2020
Publication
A series of experiments were performed in the SPARC (spray-aerosol-recombiner-combustion) test facility to simulate a hydrogen mitigation system with the actuation of a PAR (passive auto-catalytic re-combiner) and spray system. In this study the SPARC-SPRAY-PAR (SSP1) experiment is chosen to benchmark the MELCOR (a lumped-parameter code for severe accident analysis) predictions against test data. For this purpose firstly we prepared the base input model of the SPARC test vessel and tested it by a simple verification problem with well-defined boundary conditions. The implementation of a currently used PAR correlation in MELCOR is shown to be appropriate for the simulation of a PAR actuation experiment. In an SSP1 experiment the PAR is reacting with hydrogen and the spray actuation starts as soon as hydrogen injection is complete. The MELCOR simulation well predicts the pressure behavior and the gas flow affected by operating both a PAR and spray system. However the local hydrogen concentration measurement near the inlet nozzle is much higher than the volume average-value by MELCOR since high jet flow from the nozzle is dispersed in the corresponding cell volume. The experimental reproduction of the phenomena we expect or conversely the identification of phenomena we do not understand will continue to support the verification of analytical models using experimental data and to analyze the impact of spray on PAR operations in severe accident conditions.
The ‘Green’ Ni-UGSO Catalyst for Hydrogen Production under Various Reforming Regimes
Jun 2021
Publication
A new spinelized Ni catalyst (Ni-UGSO) using Ni(NO3)2·6H2O as the Ni precursor was prepared according to a less material intensive protocol. The support of this catalyst is a negative-value mining residue UpGraded Slag Oxide (UGSO) produced from a TiO2 slag production unit. Applied to dry reforming of methane (DRM) at atmospheric pressure T = 810 °C space velocity of 3400 mL/(h·g) and molar CO2/CH4 = 1.2 Ni-UGSO gives a stable over 168 h time-on-stream methane conversion of 92%. In this DRM reaction optimization study: (1) the best performance is obtained with the 10–13 wt% Ni load; (2) the Ni-UGSO catalysts obtained from two different batches of UGSO demonstrated equivalent performances despite their slight differences in composition; (3) the sulfur-poisoning resistance study shows that at up to 5.5 ppm no Ni-UGSO deactivation is observed. In steam reforming of methane (SRM) Ni-UGSO was tested at 900 °C and a molar ratio of H2O/CH4 = 1.7. In this experimental range CH4 conversion rapidly reached 98% and remained stable over 168 h time-on-stream (TOS). The same stability is observed for H2 and CO yields at around 92% and 91% respectively while H2/CO was close to 3. In mixed (dry and steam) methane reforming using a ratio of H2O/CH4 = 0.15 and CO2/CH4 = 0.97 for 74 h and three reaction temperature levels (828 °C 847 °C and 896 °C) CH4 conversion remains stable; 80% at 828 °C (26 h) 85% at 847 °C (24 h) and 95% at 896 °C (24 h). All gaseous streams have been analyzed by gas chromatography. Both fresh and used catalysts are analyzed by scanning electron microscopy-electron dispersive X-ray spectroscopy (SEM-EDXS) X-ray diffraction (XRD) and thermogravimetric analysis (TGA) coupled with mass spectroscopy (MS) and BET Specific surface. In the reducing environment of reforming such catalytic activity is mainly attributed to (a) alloys such as FeNi FeNi3 and Fe3Ni2 (reduction of NiFe2O4 FeNiAlO4) and (b) to the solid solution NiO-MgO. The latter is characterized by a molecular distribution of the catalytically active Ni phase while offering an environment that prevents C deposition due to its alkalinity.
A Review of the CFD Modeling of Hydrogen Production in Catalytic Steam Reforming Reactors
Dec 2022
Publication
Global demand for alternative renewable energy sources is increasing due to the consumption of fossil fuels and the increase in greenhouse gas emissions. Hydrogen (H2 ) from biomass gasification is a green energy segment among the alternative options as it is environmentally friendly renewable and sustainable. Accordingly researchers focus on conducting experiments and modeling the reforming reactions in conventional and membrane reactors. The construction of computational fluid dynamics (CFD) models is an essential tool used by researchers to study the performance of reforming and membrane reactors for hydrogen production and the effect of operating parameters on the methane stream improving processes for reforming untreated biogas in a catalyst-fixed bed and membrane reactors. This review article aims to provide a good CFD model overview of recent progress in catalyzing hydrogen production through various reactors sustainable steam reforming systems and carbon dioxide utilization. This article discusses some of the issues challenges and conceivable arrangements to aid the efficient generation of hydrogen from steam reforming catalytic reactions and membrane reactors of bioproducts and fossil fuels.
Simulation of a Multi-Functional Energy System for Cogeneration of Steam, Power and Hydrogen in a Coke Making Plant
Mar 2013
Publication
In this paper a multifunctional energy system (MES) is proposed for recovering energy from the extra of coke oven gas (COG) which is usually flared or vented out as a waste stream in coke making plants. The proposed system consists of a pressure swing adsorption (PSA) unit for extracting some of the hydrogen from COG a gas turbine for producing heat and power from PSA offgas and a heat recovery steam generator (HRSG) for generating the steam required by the plant's processes. o assess the performance of the system practically simulations are carried out on the basis of the design and operational conditions of Zarand Coke Making Plant in Iran. The results indicate that by utilizing about 4.39 tons of COG per hour 6.5 MW of net electric power can be approximately produced by the gas turbine which can supply the coke making plant's total electrical power demand. Furthermore through recovering heat from gas turbine's exhaust close to 57% of the plant's steam demand can be supplied by the HRSG unit. It is also found that around 350 kilograms per hour of nearly pure hydrogen (99.9% purity) at 200 bar can be produced by the PSA unit. According to the sensitivity analysis results if the hydrogen content of the coke oven gas decreases by about 10% the gross power output of the gas turbine also declines by around 5.2% due to the reduction of LHV of the PSA offgas. Moreover economic evaluation of the system shows that the payback period of the investment which is estimated at 36.1 M$ is about 5.5 years. The net present value (NPV) and internal rate of return on investment (ROI) are calculated to be 17.6% and 43.3 M$ respectively.
Operational Challenges for Low and High Temperature Electrolyzers Exploiting Curtailed Wind Energy for Hydrogen Production
Jan 2021
Publication
Understanding the system performance of different electrolyzers could aid potential investors achieve maximum return on their investment. To realize this system response characteristics to 4 different summarized data sets of curtailed renewable energy is obtained from the Irish network and was investigated using models of both a Low Temperature Electrolyzer (LTE) and a High Temperature Electrolyzer (HTE). The results indicate that statistical parameters intrinsic to the method of data extraction along with the thermal response time of the electrolyzers influence the hydrogen output. A maximum hydrogen production of 5.97 kTonne/year is generated by a 0.5 MW HTE when the electrical current is sent as a yearly average. Additionally the high thermal response time in a HTE causes a maximum change in the overall flowrate of 65.7% between the 4 scenarios when compared to 7.7% in the LTE. This evaluation of electrolyzer performance will aid investors in determining scenario specific application of P2G for maximizing hydrogen production.
Energy Technology Perspectives 2020- Special Report on Carbon Capture Utilisation and Storage
Sep 2020
Publication
Energy Technology Perspectives 2020 is a major new IEA publication focused on the technology needs and opportunities for reaching international climate and sustainable energy goals. This flagship report offers vital analysis and advice on the clean energy technologies the world needs to meet net-zero emissions objectives.
The report’s comprehensive analysis maps out the technologies needed to tackle emissions in all parts of the energy sector including areas where technology progress is still lacking such as long-distance transport and heavy industries. It shows the amount of emissions reductions that are required from electrification hydrogen bioenergy and carbon capture utilisation and storage. It also provides an assessment of emissions from existing infrastructure and what can be done to address them.
Link to Document on IEA website
The report’s comprehensive analysis maps out the technologies needed to tackle emissions in all parts of the energy sector including areas where technology progress is still lacking such as long-distance transport and heavy industries. It shows the amount of emissions reductions that are required from electrification hydrogen bioenergy and carbon capture utilisation and storage. It also provides an assessment of emissions from existing infrastructure and what can be done to address them.
Link to Document on IEA website
Tracking the Evolution of a Single Composite Particle During Redox Cycling for Application in H2 Production
Mar 2020
Publication
Composite materials consisting of metal and metal oxide phases are being researched intensively for application in various energy conversion and storage technologies. In these applications composites are often expected to operate under redox conditions at elevated temperature. The understanding of the dynamics of composite phase and morphology evolution during redox cycling is still very limited yet critical to maximising performance and increasing durability. Here we track the microstructural evolution of a single composite particle over 200 redox cycles for hydrogen production by chemical looping using multi-length scale X-ray computed tomography. We show that redox cycling triggers a centrifugal redispersion of the metal phase and a centripetal clustering of porosity both seemingly driven by the asymmetric nature of oxygen exchange in composites. We show that initially the particle develops a large amount of internal porosity which boosts activity but on the long term this facilitates structural and compositional reorganisation and eventually degradation. We also correlate the microstructural data with phase and activity analysis to identify structure-property correlations which not only provide valuable insight into the evolution of composite materials under redox conditions but also for the design of new composite materials with enhanced durability.
A Methodology for Assessing the Sustainability of Hydrogen Production from Solid Fuels
May 2010
Publication
A methodology for assessing the sustainability of hydrogen production using solid fuels is introduced in which three sustainability dimensions (ecological sociological and technological) are considered along with ten indicators for each dimension. Values for each indicator are assigned on a 10-point scale based on a high of 1 and a low of 0 depending on the characteristic of the criteria associated with each element or process utilizing data reported in the literature. An illustrative example is presented to compare two solid fuels for hydrogen production: coal and biomass. The results suggest that qualitative sustainability indicators can be reasonably defined based on evaluations of system feasibility and that adequate flexibility and comprehensiveness is provided through the use of ten indicators for each of the dimensions for every process or element involved in hydrogen production using solid fuels. Also the assessment index values suggest that biomasses have better sustainability than coals and that it may be advantageous to use coals in combination with biomass to increase their ecological and social sustainability. The sustainability assessment methodology can be made increasingly quantitative and is likely extendable to other energy systems but additional research and development is needed to lead to a more fully developed approach.
Removing the Bottleneck on Wind Power Potential to Create Liquid Fuels from Locally Available Biomass
Jun 2021
Publication
In order to reduce global greenhouse gas emissions renewable energy technologies such as wind power and solar photovoltaic power systems have recently become more widespread. However Japan as a nation faces high reliance on imported fossil fuels for electricity generation despite having great potential for further renewable energy development. The focus of this study examines untapped geographical locations in Japan’s northern most prefecture Hokkaido that possess large wind power potential. The possibility of exploiting this potential for the purpose of producing green hydrogen is explored. In particular its integration with a year-round conversion of Kraft lignin into bio-oil from nearby paper pulp mills through a near critical water depolymerization process is examined. The proposed bio-oil and aromatic chemical production as well as the process’ economics are calculated based upon the total available Kraft lignin in Hokkaido including the magnitude of wind power capacity that would be required for producing the necessary hydrogen for such a large-scale process. Green hydrogen integration with other processes in Japan and in other regions is also discussed. Finally the potential benefits and challenges are outlined from an energy policy point-of-view.
Efficient Hydrogen Production with CO2 Capture Using Gas Switching Reforming
Jul 2019
Publication
Hydrogen is a promising carbon-neutral energy carrier for a future decarbonized energy sector. This work presents process simulation studies of the gas switching reforming (GSR) process for hydrogen production with integrated CO2 capture (GSR-H2 process) at a minimal energy penalty. Like the conventional steam methane reforming (SMR) process GSR combusts the off-gas fuel from the pressure swing adsorption unit to supply heat to the endothermic reforming reactions. However GSR completes this combustion using the chemical looping combustion mechanism to achieve fuel combustion with CO2 separation. For this reason the GSR-H2 plant incurred an energy penalty of only 3.8 %-points relative to the conventional SMR process with 96% CO2 capture. Further studies showed that the efficiency penalty is reduced to 0.3 %-points by including additional thermal mass in the reactor to maintain a higher reforming temperature thereby facilitating a lower steam to carbon ratio. GSR reactors are standalone bubbling fluidized beds that will be relatively easy to scale up and operate under pressurized conditions and the rest of the process layout uses commercially available technologies. The ability to produce clean hydrogen with no energy penalty combined with this inherent scalability makes the GSR-H2 plant a promising candidate for further research.
Ordered Clustering of Single Atomic Te Vacancies in Atomically Thin PtTe2 Promotes Hydrogen Evolution Catalysis
Apr 2021
Publication
Exposing and stabilizing undercoordinated platinum (Pt) sites and therefore optimizing their adsorption to reactive intermediates offers a desirable strategy to develop highly efficient Pt-based electrocatalysts. However preparation of atomically controllable Pt-based model catalysts to understand the correlation between electronic structure adsorption energy and catalytic properties of atomic Pt sites is still challenging. Herein we report the atomically thin two-dimensional PtTe2 nanosheets with well-dispersed single atomic Te vacancies (Te-SAVs) and atomically well-defined undercoordinated Pt sites as a model electrocatalyst. A controlled thermal treatment drives the migration of the Te-SAVs to form thermodynamically stabilized ordered Te-SAV clusters which decreases both the density of states of undercoordinated Pt sites around the Fermi level and the interacting orbital volume of Pt sites. As a result the binding strength of atomically defined Pt active sites to H intermediates is effectively reduced which renders PtTe2 nanosheets highly active and stable in hydrogen evolution reaction.
Debunking the Myths of Hydrogen Production and Water Consumption
Dec 2020
Publication
In our factsheet where we debunk 3 myths around hydrogen production and water consumption: electrolysis uses vast amounts of water; electrolysis uses freshwater resources only and electrolysis is bound to create water stress in water-scarce regions.
A Review on Recent Advances in Hydrogen Energy, Fuel Cell, Biofuel and Fuel Refining via Ultrasound Process Intensification
Mar 2021
Publication
Hydrogen energy is one of the most suitable green substitutes for harmful fossil fuels and has been investigated widely. This review extensively compiles and compares various methodologies used in the production storage and usage of hydrogen. Sonochemistry is an emerging synthesis process and intensification technique adapted for the synthesis of novel materials. It manifests acoustic cavitation phenomena caused by ultrasound where higher rates of reactions occur locally. The review discusses the effectiveness of sonochemical routes in developing fuel cell catalysts fuel refining biofuel production chemical processes for hydrogen production and the physical chemical and electrochemical hydrogen storage techniques. The operational parameters and environmental conditions used during ultrasonication also influence the production rates which have been elucidated in detail. Hence this review's major focus addresses sonochemical methods that can contribute to the technical challenges involved in hydrogen usage for energy.
Enhancing Energy Recovery in Form of Biogas, from Vegetable and Fruit Wholesale Markets By-Products and Wastes, with Pretreatments
Jun 2021
Publication
Residues and by-products from vegetables and fruit wholesale markets are suitable for recovery in the form of energy through anaerobic digestion allowing waste recovery and introducing them into the circular economy. This suitability is due to their composition structural characteristics and to the biogas generation process which is stable and without inhibition. However it has been observed that the proportion of methane and the level of degradation of the substrate is low. It is decided to study whether the effect of pretreatments on the substrate is beneficial. Freezing ultrafreezing and lyophilization pretreatments are studied. A characterization of the substrates has been performed the route of action of pretreatment determined and the digestion process studied to calculate the generation of biogas methane hydrogen and the proportions among these. Also a complete analysis of the process has been performed by processing the data with mathematical and statistical methods to obtain disintegration constants and levels of degradation. It has been observed that the three pretreatments have positive effects when increasing the solubility of the substrate increasing porosity and improving the accessibility of microorganisms to the substrate. Generation of gases are greatly increased reaching a methane enrichment of 59.751%. Freezing seems to be the best pretreatment as it increases the biodegradation level the speed of the process and the disintegration constant by 306%.
Analysis of Photon-driven Solar-to-hydrogen Production Methods in the Netherlands
Oct 2021
Publication
Hydrogen is deemed necessary for the realization of a sustainable society especially when renewable energy is used to generate hydrogen. As most of the photon-driven hydrogen production methods are not commercially available yet this study has investigated the techno economic and overall performance of four different solar-to hydrogen methods and photovoltaics-based electrolysis methods in the Netherlands. It was found that the photovoltaics-based electrolysis is the cheapest option with production cost of 9.31 $/kgH2. Production cost based on photo-catalytic water splitting direct bio-photolysis and photoelectrochemical water splitting are found to be 18.32 $/kgH2 18.45 $/kgH2 and 18.98 $/kgH2 respectively. These costs are expected to drop significantly in the future. Direct bio-photolysis (potential cost of 3.10 $/kgH2) and photo-catalytic water splitting (3.12 $/kgH2) may become cheaper than photovoltaics-based electrolysis. Based on preferences of three fictional technology investors i.e. a short-term a green and a visionary investor the overall performance of these methods are determined. Photovoltaics-based electrolysis is the most ideal option with photoelectrochemical water splitting a complementary option. While photovoltaics-based electrolysis has an advantage on the short-term because it is a non-integrated energy system on the long-term this might lead to relatively higher cost and performance limitations. Photochemical water splitting are integrated energy systems and have an advantage on the long-term because they need a relatively low theoretical overpotential and benefit from increasing temperatures. Both methods show performance improvements by the use of quantum dots. Bio-photolysis can be self-sustaining and can use wastewater to produce hydrogen but sudden temperature changes could lead to performance decrease.
A Techno-Economic Analysis of Solar Hydrogen Production by Electrolysis in the North of Chile and the Case of Exportation from Atacama Desert to Japan
Aug 2020
Publication
H2 production from solar electricity in the region of the Atacama Desert – Chile – has been identified as strategical for global hydrogen exportation. In this study the full supply chain of solar hydrogen has been investigated for 2018 and projected to scenarios for 2025-2030. Multi-year hourly electrical profiles data have been used from real operating PV plants and simulated Concentrated Solar Power “CSP” plants with Thermal Energy Storage “TES” as well as commercial electricity Power Purchase Agreement “PPA” prices reported in the Chilean electricity market were considered. The Levelized Cost of Hydrogen “LCOH” of each production pathway is calculated by a case-sensitive techno-economic MATLAB/Simulink model for utility scale (multi-MW) alkaline and PEM electrolyser technologies. Successively different distribution storage and transportation configurations are evaluated based on the 2025 Japanese case study according to the declared H2 demand. Transport in the form of liquefied hydrogen (LH2) and via ammonia (NH3) carrier is compared from the port of Antofagasta CL to the port of Osaka JP.
Asymmetric Solvation of the Zinc Dimer Cation Revealed by Infrared Multiple Photon Dissociation Spectroscopy of Zn2+(H2O)n (n = 1–20)
Jun 2021
Publication
Investigating metal-ion solvation—in particular the fundamental binding interactions—enhances the understanding of many processes including hydrogen production via catalysis at metal centers and metal corrosion. Infrared spectra of the hydrated zinc dimer (Zn2+(H2O)n; n = 1–20) were measured in the O–H stretching region using infrared multiple photon dissociation (IRMPD) spectroscopy. These spectra were then compared with those calculated by using density functional theory. For all cluster sizes calculated structures adopting asymmetric solvation to one Zn atom in the dimer were found to lie lower in energy than structures adopting symmetric solvation to both Zn atoms. Combining experiment and theory the spectra show that water molecules preferentially bind to one Zn atom adopting water binding motifs similar to the Zn+(H2O)n complexes studied previously. A lower coordination number of 2 was observed for Zn2+(H2O)3 evident from the highly red-shifted band in the hydrogen bonding region. Photodissociation leading to loss of a neutral Zn atom was observed only for n = 3 attributed to a particularly low calculated Zn binding energy for this cluster size.
Hydrogen Production from Instant Noodle Wastewater by Organic Electrocatalyst Coated on PVC Surface
Mar 2020
Publication
The potential of electron-donating capability in methoxy groups of antioxidant containing protein (ACAP) as organic catalyst is restricted by its low isoelectric point. The goal of this study is to construct endure ACAP based metal-free organic catalyst for hydrogen production from electrolysis of noodle wastewater. The ACAP was coated thermomechanically on PVC sheet and its performance was tested during electrolysis of noodle wastewater. The morphological analysis phase analysis and elemental analysis of coated materials have shown a simultaneous pattern with electrolysis performances. The use of graphite flake to cover turmeric ACAP obstructs the electron to attack directly the positive charge of ACAP so that the electrocatalytic endurance increases while maintaining the hydrogen production rate. The combination of phenolic and enzymatic ACAPs is found to have the slowest reaction rate and lowest hydrogen production. The phenolic compound inhibits the enzymatic reaction.
Black TiO2 for Solar Hydrogen Conversion
Feb 2017
Publication
Titanium dioxide (TiO2 ) has been widely investigated for photocatalytic H2 evolution and photoelectrochemical (PEC) water splitting since 1972. However its wide bandgap (3.0–3.2 eV) limits the optical absorption of TiO2 for sufficient utilization of solar energy. Blackening TiO2 has been proposed as an effective strategy to enhance its solar absorption and thus the photocatalytic and PEC activities and aroused widespread research interest. In this article we reviewed the recent progress of black TiO2 for photocatalytic H2 evolution and PEC water splitting along with detailed introduction to its unique structural features optical property charge carrier transfer property and related theoretical calculations. As summarized in this review article black TiO2 could be a promising candidate for photoelectrocatalytic hydrogen generation via water splitting and continuous efforts are deserved for improving its solar hydrogen efficiency.
The Role of Critical Minerals in Clean Energy Transitions
May 2021
Publication
Minerals are essential components in many of today’s rapidly growing clean energy technologies – from wind turbines and electricity networks to electric vehicles. Demand for these minerals will grow quickly as clean energy transitions gather pace. This new World Energy Outlook Special Report provides the most comprehensive analysis to date of the complex links between these minerals and the prospects for a secure rapid transformation of the energy sector.
Alongside a wealth of detail on mineral demand prospects under different technology and policy assumptions it examines whether today’s mineral investments can meet the needs of a swiftly changing energy sector. It considers the task ahead to promote responsible and sustainable development of mineral resources and offers vital insights for policy makers including six key IEA recommendations for a new comprehensive approach to mineral security."
Link to International Energy Agency website
Alongside a wealth of detail on mineral demand prospects under different technology and policy assumptions it examines whether today’s mineral investments can meet the needs of a swiftly changing energy sector. It considers the task ahead to promote responsible and sustainable development of mineral resources and offers vital insights for policy makers including six key IEA recommendations for a new comprehensive approach to mineral security."
Link to International Energy Agency website
Hydrogen Production by Steam Reforming of DME in a Large Scale CFB Reactor. Part I: Computational Model and Predictions
Oct 2015
Publication
This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian–Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). The DME-SR reactions scheme and kinetics in the presence of a bifunctional catalyst of CuO/ZnO/Al2O3+ZSM-5 were incorporated in the model using in-house developed user-defined function. The model was validated by comparing the predictions with experimental data from the literature. The results revealed for the first time detailed CFB reactor hydrodynamics gas residence time temperature distribution and product gas composition at a selected operating condition of 300 °C and steam to DME mass ratio of 3 (molar ratio of 7.62). The spatial variation in the gas species concentrations suggests the existence of three distinct reaction zones but limited temperature variations. The DME conversion and hydrogen yield were found to be 87% and 59% respectively resulting in a product gas consisting of 72 mol% hydrogen. In part II of this study the model presented here will be used to optimize the reactor design and study the effect of operating conditions on the reactor performance and products.
The BioSCWG Project: Understanding the Trade-Offs in the Process and Thermal Design of Hydrogen and Synthetic Natural Gas Production
Oct 2016
Publication
This article presents a summary of the main findings from a collaborative research project between Aalto University in Finland and partner universities. A comparative process synthesis modelling and thermal assessment was conducted for the production of Bio-synthetic natural gas (SNG) and hydrogen from supercritical water refining of a lipid extracted algae feedstock integrated with onsite heat and power generation. The developed reactor models for product gas composition yield and thermal demand were validated and showed conformity with reported experimental results and the balance of plant units were designed based on established technologies or state-of-the-art pilot operations. The poly-generative cases illustrated the thermo-chemical constraints and design trade-offs presented by key process parameters such as plant organic throughput supercritical water refining temperature nature of desirable coproducts downstream indirect production and heat recovery scenarios. The evaluated cases favoring hydrogen production at 5 wt. % solid content and 600 ◦C conversion temperature allowed higher gross syngas and CHP production. However mainly due to the higher utility demands the net syngas production remained lower compared to the cases favoring BioSNG production. The latter case at 450 ◦C reactor temperature 18 wt. % solid content and presence of downstream indirect production recorded 66.5% 66.2% and 57.2% energetic fuel-equivalent and exergetic efficiencies respectively
Production of Hydrogen by Chemical Looping Reforming of Methane and Biogas using a Reactive and Durable Cu-based Oxygen Carrier
Apr 2022
Publication
The objective of this work was to assess the suitability of a synthetic Cu-based oxygen carrier in a continuous pilot plant for the production of blue and green hydrogen through the autothermal Chemical Looping Reforming (CLRa). In CLRa methane is converted to a H2 + CO mixture through partial oxidation and reforming reactions in the fuel reactor. The degree of the partial oxidation of methane was defined by controlling the oxygen flow in the air reactor. Steam was used as reforming gas in natural gas to produce blue H2 but the existing CO2 in biogas was the reforming gas to produce green H2. Operating at 950 ◦C in the fuel and air reactors CH4 conversion and H2 yield parameters were 96 % and 2.60 mol of H2 per mole of CH4 respectively. These experimental results were close to the theoretical values that could be achieved in the CLRa process. Furthermore the physico-chemical characterization of the samples extracted from the pilot plant throughout the experimental campaign revealed that the Cu-based oxygen carrier maintained its mechanical integrity and chemical stability under harsh operating conditions. Therefore it can be concluded that Cu-based oxygen carriers can be considered a promising alternative to Ni-based materials for the production of blue and green hydrogen through the CLRa process.
A Mountain to Climb? Tracking Progress in Scaling Up Renewable Gas Production in Europe
Oct 2019
Publication
In the last couple of years there has been increasing recognition by key players in the European gas industry that to mitigate the risk of terminal decline in the context of a decarbonising energy system there will need to be rapid scale up of decarbonised gas. This has led to several projections of the scale of decarbonised gas which could potentially be supplied by 2030 2040 or 2050. This paper joint with the Sustainable Gas Institute at Imperial College London considers the very significant rate of scale up and the significant cost reductions contemplated by such projections. Based on a database of actual announced projects (both committed and in earlier stages of development) for production of decarbonised gas it then considers the extent to which project activity is consistent with meeting the ambitious projections. It identifies a significant gap in current levels of activity largely because there is not yet sufficient economic incentive for investors to develop the required projects. It is intended that this paper will form the basis of continued tracking of the level of activity over the coming years to help inform industry players of further actions which may be required.
Hydrogen Production by Fluidized Bed Reactors: A Quantitative Perspective Using the Supervised Machine Learning Approach
Jul 2021
Publication
The current hydrogen generation technologies especially biomass gasification using fluidized bed reactors (FBRs) were rigorously reviewed. There are involute operational parameters in a fluidized bed gasifier that determine the anticipated outcomes for hydrogen production purposes. However limited reviews are present that link these parametric conditions with the corresponding performances based on experimental data collection. Using the constructed artificial neural networks (ANNs) as the supervised machine learning algorithm for data training the operational parameters from 52 literature reports were utilized to perform both the qualitative and quantitative assessments of the performance such as the hydrogen yield (HY) hydrogen content (HC) and carbon conversion efficiency (CCE). Seven types of operational parameters including the steam-to-biomass ratio (SBR) equivalent ratio (ER) temperature particle size of the feedstock residence time lower heating value (LHV) and carbon content (CC) were closely investigated. Six binary parameters have been identified to be statistically significant to the performance parameters (hydrogen yield (HY)) hydrogen content (HC) and carbon conversion efficiency (CCE) by analysis of variance (ANOVA). The optimal operational conditions derived from the machine leaning were recommended according to the needs of the outcomes. This review may provide helpful insights for researchers to comprehensively consider the operational conditions in order to achieve high hydrogen production using fluidized bed reactors during biomass gasification.
Earth-Abundant Electrocatalysts for Water Splitting: Current and Future Directions
Mar 2021
Publication
Of all the available resources given to mankind the sunlight is perhaps the most abundant renewable energy resource providing more than enough energy on earth to satisfy all the needs of humanity for several hundred years. Therefore it is transient and sporadic that poses issues with how the energy can be harvested and processed when the sun does not shine. Scientists assume that electro/photoelectrochemical devices used for water splitting into hydrogen and oxygen may have one solution to solve this hindrance. Water electrolysis-generated hydrogen is an optimal energy carrier to store these forms of energy on scalable levels because the energy density is high and no air pollution or toxic gas is released into the environment after combustion. However in order to adopt these devices for readily use they have to be low-cost for manufacturing and operation. It is thus crucial to develop electrocatalysts for water splitting based on low-cost and land-rich elements. In this review I will summarize current advances in the synthesis of low-cost earth-abundant electrocatalysts for overall water splitting with a particular focus on how to be linked with photoelectrocatalytic water splitting devices. The major obstacles that persist in designing these devices. The potential future developments in the production of efficient electrocatalysts for water electrolysis are also described.
Scenario-Based Techno-Economic Analysis of Steam Methane Reforming Process for Hydrogen Production
Jun 2021
Publication
Steam methane reforming (SMR) process is regarded as a viable option to satisfy the growing demand for hydrogen mainly because of its capability for the mass production of hydrogen and the maturity of the technology. In this study an economically optimal process configuration of SMR is proposed by investigating six scenarios with different design and operating conditions including CO2 emission permits and CO2 capture and sale. Of the six scenarios the process configuration involving CO2 capture and sale is the most economical with an H2 production cost of $1.80/kg-H2. A wide range of economic analyses is performed to identify the tradeoffs and cost drivers of the SMR process in the economically optimal scenario. Depending on the CO2 selling price and the CO2 capture cost the economic feasibility of the SMR-based H2 production process can be further improved.
Recent Progress in Mixed-Matrix Membranes for Hydrogen Separation
Aug 2021
Publication
Membrane separation is a compelling technology for hydrogen separation. Among the different types of membranes used to date the mixed-matrix membranes (MMMs) are one of the most widely used approaches for enhancing separation performances and surpassing the Robeson upper bound limits for polymeric membranes. In this review we focus on the recent progress in MMMs for hydrogen separation. The discussion first starts with a background introduction of the current hydrogen generation technologies followed by a comparison between the membrane technology and other hydrogen purification technologies. Thereafter state-of-the-art MMMs comprising emerging filler materials that include zeolites metal-organic frameworks covalent organic frameworks and graphene-based materials are highlighted. The binary filler strategy which uses two filler materials to create synergistic enhancements in MMMs is also described. A critical evaluation on the performances of the MMMs is then considered in context before we conclude with our perspectives on how MMMs for hydrogen separation can advance moving forward.
Production of Advanced Fuels Through Integration of Biological, Thermo-Chemical and Power to Gas Technologies in a Circular Cascading Bio-Based System
Sep 2020
Publication
In the transition to a climate neutral future the transportation sector needs to be sustainably decarbonized. Producing advanced fuels (such as biomethane) and bio-based valorised products (such as pyrochar) may offer a solution to significantly reduce greenhouse gas (GHG) emissions associated with energy and agricultural circular economy systems. Biological and thermochemical bioenergy technologies together with power to gas (P2G) systems can generate green renewable gas which is essential to reduce the GHG footprint of industry. However each technology faces challenges with respect to sustainability and conversion efficiency. Here this study identifies an optimal pathway leading to a sustainable bioenergy system where the carbon released in the fuel is offset by the GHG savings of the circular bio-based system. It provides a state-of-the-art review of individual technologies and proposes a bespoke circular cascading bio-based system with anaerobic digestion as the key platform integrating electro-fuels via P2G systems and value-added pyrochar via pyrolysis of solid digestate. The mass and energy analysis suggests that a reduction of 11% in digestate mass flow with the production of pyrochar bio-oil and syngas and an increase of 70% in biomethane production with the utilization of curtailed or constrained electricity can be achieved in the proposed bio-based system enabling a 70% increase in net energy output as compared with a conventional biomethane system. However the carbon footprint of the electricity from which the hydrogen is sourced is shown to be a critical parameter in assessing the GHG balance of the bespoke system.
A Hybrid Intelligent Model to Predict the Hydrogen Concentration in the Producer Gas from a Downdraft Gasifier
Apr 2022
Publication
This research work presents an artificial intelligence approach to predicting the hydrogen concentration in the producer gas from biomass gasification. An experimental gasification plant consisting of an air-blown downdraft fixed-bed gasifier fueled with exhausted olive pomace pellets and a producer gas conditioning unit was used to collect the whole dataset. During an extensive experimental campaign the producer gas volumetric composition was measured and recorded with a portable syngas analyzer at a constant time step of 10 seconds. The resulting dataset comprises nearly 75 hours of plant operation in total. A hybrid intelligent model was developed with the aim of performing fault detection in measuring the hydrogen concentration in the producer gas and still provide reliable values in the event of malfunction. The best performing hybrid model comprises six local internal submodels that combine artificial neural networks and support vector machines for regression. The results are remarkably satisfactory with a mean absolute prediction error of only 0.134% by volume. Accordingly the developed model could be used as a virtual sensor to support or even avoid the need for a real sensor that is specific for measuring the hydrogen concentration in the producer gas.
Nickel Sulfides Supported by Carbon Spheres as Efficient Catalysts for Hydrogen Evolution Reaction
Jun 2021
Publication
Ni3S2 and NiS supported on carbon spheres are successfully synthesized by a facile hydrothermal method. And then a series of physical characterizations included XRD (X-ray diffraction) EDS (energy dispersive spectroscopy) FESEM (field emission scanning electron microscopy) and XPS (X-ray photo-electron spectroscopy) were used to analyze the samples. XRD was used to confirm that NiNi3S2 S2 and NiS were successfully fabricated. FESEM indicated that Ni3S2 and NiS disperse well on carbon spheres. Electrochemical tests showed that nickel sulfides supported by carbon spheres exhibited excellent hydrogen evolution performance. The excellent catalytic activity is attributed to the synergistic effect of carbon spheres and transition metal sulfides of which the carbon spheres act to enhance the electrical conductivity and the dispersion of Ni3S2 and NiS thus providing more active sites for the hydrogen evolution reaction.
PEM Fuel Cell Performance with Solar Air Preheating
Feb 2020
Publication
Proton Exchange Membrane Fuel Cells (PEMFC) have proven to be a promising energy conversion technology in various power applications and since it was developed it has been a potential alternative over fossil fuel-based engines and power plants all of which produce harmful by-products. The inlet air coolant and reactants have an important effect on the performance degradation of the PEMFC and certain power outputs. In this work a theoretical model of a PEM fuel cell with solar air heating system for the preheating hydrogen of PEM fuel cell to mitigate the performance degradation when the fuel cell operates in cold environment is proposed and evaluated by using energy analysis. Considering these heating and energy losses of heat generation by hydrogen fuel cells the idea of using transpired solar collectors (TSC) for air preheating to increase the inlet air temperature of the low-temperature fuel cell could be a potential development. The aim of the current article is applying solar air preheating for the hydrogen fuel cells system by applying TSC and analyzing system performance. Results aim to attention fellow scholars as well as industrial engineers in the deployment of solar air heating together with hydrogen fuel cell systems that could be useful for coping with fossil fuel-based power supply systems.
Thermal Efficiency of On-site, Small-scale Hydrogen Production Technologies using Liquid Hydrocarbon Fuels in Comparison to Electrolysis a Case Study in Norway
Oct 2018
Publication
The main goal of this study was to assess the energy efficiency of a small-scale on-site hydrogen production and dispensing plant for transport applications. The selected location was the city of Narvik in northern Norway where the hydrogen demand is expected to be 100 kg/day. The investigated technologies for on-site hydrogen generation starting from common liquid fossil fuels such as heavy naphtha and diesel were based on steam reforming and partial oxidation. Water electrolysis derived by renewable energy was also included in the comparison. The overall thermal efficiency of the hydrogen station was computed including compression and miscellaneous power consumption.
Project Cavendish - National Grid Gas Transmission
Sep 2020
Publication
The Isle of Grain (IoG) presents a technically feasible commercially viable strategic location to build and operate a hydrogen production facility which would be a key enabler to the UK meeting the Net Zero 2050 target.
As highlighted in the ‘Net Zero – The UK’s contribution to stopping global warming’ report published by The Committee on Climate Change in May 2019 hydrogen is set to have a major part to play in reducing UK carbon dioxide emissions. Carbon Capture and Storage (CCS) is also seen as essential to support those supplies.
The report further recognises that this will involve increased investments and that CCS and hydrogen will require both capital funding and revenue support.
For hydrogen to have a part to play in the decarbonisation of London and the south east of England a large-scale hydrogen production facility will be required which will provide a multi vector solution through the decarbonisation of the gas grid.
This report and any attachment is freely available on the ENA Smarter Networks Portal here. IGEM Members can download the report and any attachment directly by clicking on the pdf icon above.
As highlighted in the ‘Net Zero – The UK’s contribution to stopping global warming’ report published by The Committee on Climate Change in May 2019 hydrogen is set to have a major part to play in reducing UK carbon dioxide emissions. Carbon Capture and Storage (CCS) is also seen as essential to support those supplies.
The report further recognises that this will involve increased investments and that CCS and hydrogen will require both capital funding and revenue support.
For hydrogen to have a part to play in the decarbonisation of London and the south east of England a large-scale hydrogen production facility will be required which will provide a multi vector solution through the decarbonisation of the gas grid.
This report and any attachment is freely available on the ENA Smarter Networks Portal here. IGEM Members can download the report and any attachment directly by clicking on the pdf icon above.
Massive H2 Production With Nuclear Heating, Safety Approach For Coupling A VHTR With An Iodine Sulfur Process Cycle
Sep 2005
Publication
In the frame of a sustainable development investigations dealing with massive Hydrogen production by means of nuclear heating are carried out at CEA. For nuclear safety thermodynamic efficiency and waste minimization purposes the technological solution privileged is the coupling of a gas cooled Very High Temperature Reactor (VHTR) with a plant producing Hydrogen from an Iodine/Sulfur (I/S) thermochemical cycle. Each of the aforementioned facilities presents different risks resulting from the operation of a nuclear reactor (VHTR) and from a chemical plant including Hydrogen other flammable and/or explosible substances as well as toxic ones. Due to these various risks the safety approach is an important concern. Therefore this paper deals with the preliminary CEA investigations on the safety issues devoted to the whole plant focusing on the safety questions related to the coupling between the nuclear reactor and the Hydrogen production facility. Actually the H2 production process and the energy distribution network between the plants are currently at a preliminary design stage. A general safety approach is proposed based on a Defence In Depth (DID) principle permitting to analyze all the system configurations successively in normal incidental and accidental expected operating conditions. More precisely the dynamic answer of an installation to a perturbation affecting the other one during the previous conditions as well as the potential aggressions of the chemical plant towards the nuclear reactor have to be considered. The methodology presented in this paper is intended to help the designer to take into account the coupling safety constraints and to provide some recommendations on the global architecture of both plants especially on their coupling system. As a result the design of a VHTR combined to a H2 production process will require an iterative process between design and safety requirements.
Recent Progress in the Steam Reforming of Bio-Oil for Hydrogen Production: A Review of Operating Parameters, Catalytic Systems and Technological Innovations
Dec 2021
Publication
The present review focuses on the production of renewable hydrogen through the catalytic steam reforming of bio-oil the liquid product of the fast pyrolysis of biomass. Although in theory the process is capable of producing high yields of hydrogen in practice certain technological issues require radical improvements before its commercialization. Herein we illustrate the fundamental knowledge behind the technology of the steam reforming of bio-oil and critically discuss the major factors influencing the reforming process such as the feedstock composition the reactor design the reaction temperature and pressure the steam to carbon ratio and the hour space velocity. We also emphasize the latest research for the best suited reforming catalysts among the specific groups of noble metal transition metal bimetallic and perovskite type catalysts. The effect of the catalyst preparation method and the technological obstacle of catalytic deactivation due to coke deposition metal sintering metal oxidation and sulfur poisoning are addressed. Finally various novel modified steam reforming techniques which are under development are discussed such as the in-line two-stage pyrolysis and steam reforming the sorption enhanced steam reforming (SESR) and the chemical looping steam reforming (CLSR). Moreover we argue that while the majority of research studies examine hydrogen generation using different model compounds much work must be done to optimally treat the raw or aqueous bio-oil mixtures for efficient practical use. Moreover further research is also required on the reaction mechanisms and kinetics of the process as these have not yet been fully understood.
High Purity, Self-sustained, Pressurized Hydrogen Production from Ammonia in a Catalytic Membrane Reactor
Dec 2021
Publication
The combination of catalytic decomposition of ammonia and in situ separation of hydrogen holds great promise for the use of ammonia as a clean energy carrier. However finding the optimal catalyst – membrane pair and operation conditions have proved challenging. Here we demonstrate that cobalt-based catalysts for ammonia decomposition can be efficiently 2 used together with a Pd-Au based membrane to produce high purity hydrogen at elevated pressure. Compared to a conventional packed bed reactor the membrane reactor offers several operational advantages that result in energetic and economic benefits. The robustness and durability of the combined system has been demonstrated for more than 1000 h on stream yielding a very pure hydrogen stream (>99.97 % H2) and recovery (>90 %). When considering the required hydrogen compression for storage/utilization and environmental issues the combined system offers the additional advantage of production of hydrogen at moderate pressures along with full ammonia conversion. Altogether our results demonstrate the possibility of deploying high pressure (350 bar) hydrogen generators from ammonia with H2 efficiencies of circa 75% without any external energy input and/or derived CO2 emissions.
Experimental Characterization and Energy Performance Assessment of a Sorption-Enhanced Steam–Methane Reforming System
Aug 2021
Publication
The production of blue hydrogen through sorption-enhanced processes has emerged as a suitable option to reduce greenhouse gas emissions. Sorption-enhanced steam–methane reforming (SESMR) is a process intensification of highly endothermic steam–methane reforming (SMR) ensured by in situ carbon capture through a solid sorbent making hydrogen production efficient and more environmentally sustainable. In this study a comprehensive energy model of SESMR was developed to carry out a detailed energy characterization of the process with the aim of filling a current knowledge gap in the literature. The model was applied to a bench-scale multicycle SESMR/sorbent regeneration test to provide an energy insight into the process. Besides the experimental advantages of higher hydrogen concentration (90 mol% dry basis 70 mol% wet basis) and performance of CO2 capture the developed energy model demonstrated that SESMR allows for substantially complete energy self-sufficiency through the process. In comparison to SMR with the same process conditions (650 ◦C 1 atm) performed in the same experimental rig SESMR improved the energy efficiency by about 10% further reducing energy needs.
Dynamic Model to Expand Energy Storage in Form of Battery and Hydrogen Production Using Solar Powered Water Electrolysis for Off Grid Communities
Feb 2022
Publication
In this model we used a 50 WP photovoltaic panel to produce electrical energy. This electricity production was used directly and stored in a battery. In this design we coupled batteries and hydrogen as a means of storing energy. In case of overcharging the battery it will be attached with water electrolysis to convert the excess amount of chemical energy of the battery into hydrogen energy storage. Hydrogen will be stored as a compacted gas and in chemical storage. We used PEM (proton exchange membrane) electrolysis technologies to breakdown water molecules into hydrogen and oxygen which were then stored in the designed tanks. Different supply voltages were used in our practical readings with an average gaining of 22.8 mL/min on a voltage supply of 2. While using Ansys simulation software we extrapolated hydrogen production until reaching 300 mL/min on 12 V of supply (which represents 220% higher production). By using the second phase of this model hydrogen energy was converted back into electrical energy with the help of a PEM (proton exchange membrane) fuel cell when needed. This model explores the feasibility of energy storage in the form of hydrogen and chemical energy for off-grid communities and remote areas comprising batteries water electrolysis and fuel cells. The main purpose of hydrogen storage in this system is to store and handle the extra energy of system produced through PV panel and utilize it for any desired requirements.
Experimental and Theoretical Insights to Demonstrate the Hydrogen Evolution Activity of Layered Platinum Dichalcogenides Electrocatalysts
Mar 2021
Publication
Hydrogen is a highly efficient and clean renewable energy source and water splitting through electrocatalytic hydrogen evolution is a most promising approach for hydrogen generation. Layered transition metal dichalcogenides-based nano-structures have recently attracted significant interest as robust and durable catalysts for hydrogen evolution. We systematically investigated the platinum (Pt) based dichalcogenides (PtS2 PtSe2 and PtTe2) as highly energetic and robust hydrogen evolution electrocatalysts. PtTe2 catalyst unveiled the rapid hydrogen evolution process with the low overpotentials of 75 and 92 mV (vs. RHE) at a current density of 10 mA cm−2 and the small Tafel slopes of 64 and 59 mV/dec in acidic and alkaline medium respectively. The fabricated PtTe2 electrocatalyst explored a better catalytic activity than PtS2 and PtSe2. The density functional theory estimations explored that the observed small Gibbs free energy for H-adsorption of PtTe2 was given the prominent role to achieve the superior electrocatalytic and excellent stability activity towards hydrogen evolution due to a smaller bandgap and the metallic nature. We believe that this work will offer a key path to use Pt based dichalcogenides for hydrogen evolution electrocatalysts.
Thermodynamic Assessment of a Solar-Driven Integrated Membrane Reactor for Ethanol Steam Reforming
Nov 2020
Publication
To efficiently convert and utilize intermittent solar energy a novel solar-driven ethanol steam reforming (ESR) system integrated with a membrane reactor is proposed. It has the potential to convert low-grade solar thermal energy into high energy level chemical energy. Driven by chemical potential hydrogen permeation membranes (HPM) can separate the generated hydrogen and shift the ESR equilibrium forward to increase conversion and thermodynamic efficiency. The thermodynamic and environmental performances are analyzed via numerical simulation under a reaction temperature range of 100–400 ◦C with permeate pressures of 0.01–0.75 bar. The highest theoretical conversion rate is 98.3% at 100 ◦C and 0.01 bar while the highest first-law efficiency solar-to-fuel efficiency and exergy efficiency are 82.3% 45.3% and 70.4% at 215 ◦C and 0.20 bar. The standard coal saving rate (SCSR) and carbon dioxide reduction rate (CDRR) are maximums of 101 g·m−2 ·h −1 and 247 g·m−2 ·h −1 at 200 ◦C and 0.20 bar with a hydrogen generation rate of 22.4 mol·m−2 ·h −1 . This study illustrates the feasibility of solar-driven ESR integrated with a membrane reactor and distinguishes a novel approach for distributed hydrogen generation and solar energy utilization and upgradation.
Review of Hydrogen Production Techniques from Water Using Renewable Energy Sources and Its Storage in Salt Caverns
Feb 2022
Publication
Hydrogen is becoming an increasingly important energy carrier in sector integration for fuel cell transportation heat and electricity. Underground salt caverns are one of the most promising ways to store the hydrogen obtained from water electrolysis using power generation from renewable energy sources (RES). At the same time the production of hydrogen can be used to avoid energy curtailments during times of low electricity demand or low prices. The stored hydrogen can also be used during times of high energy demand for power generation e.g. with fuel cells to cover the fluctuations and shortages caused by low RES generation. This article presents an overview of the techniques that were used and proposed for using excess energy from RES for hydrogen production from water and its storage techniques especially in underground salt caverns for the aforementioned purpose and its feasibility. This paper compares and summarizes the competing technologies based on the current state-of-the-art identifies some of the difficulties in hydrogen production and storage and discusses which technology is the most promising. The related analysis compares cost and techno-economic feasibility with regard to hydrogen production and storage systems. The paper also identifies the potential technical challenges and the limitations associated with hydrogen integration into the power grid.
Discussion on the Feasibility of the Integration of Wind Power and Coal Chemical Industries for Hydrogen Production
Oct 2021
Publication
To improve the utilization rate of the energy industry and reduce high energy consumption and pollution caused by coal chemical industries in north western China a planning scheme of a wind‐coal coupling energy system was developed. This scheme involved the analysis method evaluation criteria planning method and optimization operation check for the integration of a comprehensive evaluation framework. A system was established to plan the total cycle revenue to maximize the net present value of the goal programming model and overcome challenges associated with the development of new forms of energy. Subsequently the proposed scheme is demonstrated using a 500‐MW wind farm. The annual capacity of a coal‐to‐methanol system is 50000. Results show that the reliability of the wind farm capacity and the investment subject are the main factors affecting the feasibility of the wind‐coal coupled system. Wind power hydrogen production generates O2 and H2 which are used for methanol preparation and electricity production in coal chemical systems respectively. Considering electricity price constraints and environmental benefits a methanol production plant can construct its own wind farm matching its output to facilitate a more economical wind‐coal coupled system. Owing to the high investment cost of wind power plants an incentive mechanism for saving energy and reducing emissions should be provided for the wind‐ coal coupled system to ensure economic feasibility and promote clean energy transformation.
Converting Sewage Water into H2 Fuel Gas Using Cu/CuO Nanoporous Photocatalytic Electrodes
Feb 2022
Publication
This work reports on H2 fuel generation from sewage water using Cu/CuO nanoporous (NP) electrodes. This is a novel concept for converting contaminated water into H2 fuel. The preparation of Cu/CuO NP was achieved using a simple thermal combustion process of Cu metallic foil at 550 ◦C for 1 h. The Cu/CuO surface consists of island-like structures with an inter-distance of 100 nm. Each island has a highly porous surface with a pore diameter of about 250 nm. X-ray diffraction (XRD) confirmed the formation of monoclinic Cu/CuO NP material with a crystallite size of 89 nm. The prepared Cu/CuO photoelectrode was applied for H2 generation from sewage water achieving an incident to photon conversion efficiency (IPCE) of 14.6%. Further the effects of light intensity and wavelength on the photoelectrode performance were assessed. The current density (Jph) value increased from 2.17 to 4.7 mA·cm−2 upon raising the light power density from 50 to 100 mW·cm−2 . Moreover the enthalpy (∆H*) and entropy (∆S*) values of Cu/CuO electrode were determined as 9.519 KJ mol−1 and 180.4 JK−1 ·mol−1 respectively. The results obtained in the present study are very promising for solving the problem of energy in far regions by converting sewage water to H2 fuel.
Effect of Au Plasmonic Material on Poly M-Toluidine for Photoelectrochemical Hydrogen Generation from Sewage Water
Feb 2022
Publication
This study provides H2 gas as a renewable energy source from sewage water splitting reaction using a PMT/Au photocathode. So this study has a dual benefit for hydrogen generation; at the same time it removes the contaminations of sewage water. The preparation of the PMT is carried out through the polymerization process from an acid medium. Then the Au sputter was carried out using the sputter device under different times (1 and 2 min) for PMT/Au-1 min and PMT/Au-2min respectively. The complete analyses confirm the chemical structure such as XRD FTIR HNMR SEM and Vis-UV optical analyses. The prepared electrode PMT/Au is used for the hydrogen generation reaction using Na2S2O3 or sewage water as an electrolyte. The PMT crystalline size is 15 nm. The incident photon to current efficiency (IPCE) efficiency increases from 2.3 to 3.6% (at 390 nm) and the number of H2 moles increases from 8.4 to 33.1 mmol h−1 cm−2 for using Na2S2O3 and sewage water as electrolyte respectively. Moreover all the thermodynamic parameters such as activation energy (Ea) enthalpy (∆H*) and entropy (∆S*) were calculated; additionally a simple mechanism is mentioned for the water-splitting reaction.
Comparison of Hydrogen Powertrains with the Battery Powered Electric Vehicle and Investigation of Small-Scale Local Hydrogen Production Using Renewable Energy
Jan 2021
Publication
Climate change is one of the major problems that people face in this century with fossil fuel combustion engines being huge contributors. Currently the battery powered electric vehicle is considered the predecessor while hydrogen vehicles only have an insignificant market share. To evaluate if this is justified different hydrogen power train technologies are analyzed and compared to the battery powered electric vehicle. Even though most research focuses on the hydrogen fuel cells it is shown that despite the lower efficiency the often-neglected hydrogen combustion engine could be the right solution for transitioning away from fossil fuels. This is mainly due to the lower costs and possibility of the use of existing manufacturing infrastructure. To achieve a similar level of refueling comfort as with the battery powered electric vehicle the economic and technological aspects of the local small-scale hydrogen production are being investigated. Due to the low efficiency and high prices for the required components this domestically produced hydrogen cannot compete with hydrogen produced from fossil fuels on a larger scale
High Performance of Biohydrogen Production in Packed-Filter Bioreactor via Optimizing Packed-Filter Position
Jul 2021
Publication
In this present investigation a packed-filter bioreactor was employed to produce hydrogen utilizing an expired soft drink as a substrate. The effects of feeding substrate concentrations ranging from 19.51 10.19 5.34 3.48 to 2.51 g total sugar/L were examined and the position of the packed filter installed in the bioreactor at dimensionless heights (h/H) of 1/4 2/4 3/4 and 4/4 was studied. The results revealed that with a substrate concentration of 20 g total sugar/L and a hydraulic retention time (HRT) of 1 h a packed filter placed at the half-height position of the bioreactor (h/H 2/4) has the optimal hydrogen production rate hydrogen yield and average biomass concentration in the bioreactor resulting in 55.70 ± 2.42 L/L/d 0.90 ± 0.06 mol H2/mol hexose and 17.86 ± 1.09 g VSS/L. When feeding substrate concentrations varied from 20 10 to 5 g total sugar/L with the packed-filter position at h/H 2/4 Clostridium sp. Clostridium tyrobutyricum and Bifidobacterium crudilactis were the predominant bacteria community. Finally it was discovered that the packed-filter bioreactor can produce stable hydrogen in high-strength organic effluent.
Optimal Operation of the Hydrogen-based Energy Management System with P2X Demand Response and Ammonia Plant
Jul 2021
Publication
Hydrogen production is the key in utilizing an excess renewable energy. Many studies and projects looked at the energy management systems (EMSs) that allow to couple hydrogen production with renewable generation. In the majority of these studies however hydrogen demand is either produced for powering fuel cells or sold to the external hydrogen market. Hydrogen demand from actual industrial plants is rarely considered. In this paper we propose an EMS based on the industrial cluster of GreenLab Skive (GLS) that can minimize the system’s operational cost or maximize its green hydrogen production. EMS utilizes a conventional and P2X demand response (DR) flexibility from electrolysis plant hydrogen storage tank electric battery and hydrogen-consuming plants to design the optimal schedule with maximized benefits. A potential addition to the existing components at GLS - an ammonia plant is modelled to identify its P2X potential and assess the economic viability of its construction. The results show a potential reduction of 51.5–61.6% for the total operational cost of the system and an increase of the share of green hydrogen by 10.4–37.6% due to EMS operation.
Goal and Scope in Life Cycle Sustainability Analysis: The Case of Hydrogen Production from Biomass
Aug 2014
Publication
The framework for life cycle sustainability analysis (LCSA) developed within the project CALCAS (Co-ordination Action for innovation in Life-Cycle Analysis for Sustainability) is introducing a truly integrated approach for sustainability studies. However it needs to be further conceptually refined and to be made operational. In particular one of the gaps still hindering the adoption of integrated analytic tools for sustainability studies is the lack of a clear link between the goal and scope definition and the modeling phase. This paper presents an approach to structure the goal and scope phase of LCSA so as to identify the relevant mechanisms to be further detailed and analyzed in the modeling phase. The approach is illustrated with an on-going study on a new technology for the production of high purity hydrogen from biomass to be used in automotive fuel cells.
Optimal Strategies of Deployment of Far Offshore Co-located Wind-wave Energy Farms
Nov 2021
Publication
The most profitable offshore energy resources are usually found away from the coast. Nevertheless the accessibility and grid integration in those areas are more complicated. To avoid this problematic large scale hydrogen production is being promoted for far offshore applications. The main objective of this paper is to analyze the ability of wave energy converters to maximize hydrogen production in hybrid wind and wave far offshore farms. To that end wind and wave resource data are obtained from ERA5 for different locations in the Atlantic ocean and a Maximum Covariance Analysis is proposed for the selection of the most representative locations. Furthermore the suitability of different sized wave energy converters for auxiliary hydrogen production in the far offshore wind farms is also analysed. On that account the hydrodynamic parameters of the oscillating bodies are obtained via simulations with a Boundary Element Method based code and their operation is modelled using the software tool Matlab. The combination of both methodologies enables to perform a realistic assessment of the contribution of the wave energy converters to the hydrogen generation of an hybrid energy farm especially during those periods when the wind turbines would be stopped due to the variability of the wind. The obtained results show a considerable hydrogen generation capacity of the wave energy converters up to 6.28% of the wind based generation which could remarkably improve the efficiency of the far offshore farm and bring important economical profit. Wave energy converters are observed to be most profitable in those farms with low covariance between wind and waves where the disconnection times of the wind turbines are prone to be more prolonged but the wave energy is still usable. In such cases a maximum of 101.12 h of equivalent rated production of the wind turbine has been calculated to be recovered by the wave energy converters.
Hydrogen-Rich Gas Production from Two-Stage Catalytic Pyrolysis of Pine Sawdust with Nano-NiO/Al2O3 Catalyst
Feb 2022
Publication
Hydrogen production from biomass pyrolysis is economically and technologically attractive from the perspectives of energy and the environment. The two-stage catalytic pyrolysis of pine sawdust for hydrogen-rich gas production is investigated using nano-NiO/Al2O3 as the catalyst at high temperatures. The influences of residence time (0–30 s) and catalytic temperature (500–800 ◦C) on pyrolysis performance are examined in the distribution of pyrolysis products gas composition and gas properties. The results show that increasing the residence time decreased the solid and liquid products but increased gas products. Longer residence times could promote tar cracking and gas-phase conversion reactions and improve the syngas yield H2/CO ratio and carbon conversion. The nano-NiO/A12O3 exhibits excellent catalytic activity for tar removal with a tar conversion rate of 93% at 800 ◦C. The high catalytic temperature could significantly improve H2 and CO yields by enhancing the decomposition of tar and gas-phase reactions between CO2 and CH4 . The increasing catalytic temperature increases the dry gas yield and carbon conversion but decreases the H2/CO ratio and low heating value.
Interfacial Confinement of Ni-V2O3 in Molten Salts for Enhanced Electrocatalytic Hydrogen Evolution
Apr 2020
Publication
Implementation of non-precious electrocatalysts is key-enabling for water electrolysis to relieve challenges in energy and environmental sustainability. Self-supporting Ni-V2O3.electrodes consisting of nanostrip-like V2O3.perpendicularly anchored on Ni meshes are herein constructed via the electrochemical reduction of soluble NaVO3 in molten salts for enhanced electrocatalytic hydrogen evolution. Such a special configuration in morphology and composition creates a well confined interface between Ni and V2O3. Experimental and Density-Functional-Theory results confirm that the synergy between Ni and V2O3.accelerates the dissociation of H2O for forming hydrogen intermediates and enhances the combination of H* for generating H2.
Development of Visible-Light-Driven Rh–TiO2-CeO2 Hybrid Photocatalysts for Hydrogen Production
Jul 2021
Publication
Visible-light-driven hydrogen production through photocatalysis has attracted enormous interest owing to its great potential to address energy and environmental issues. However photocatalysis possesses several limitations to overcome for practical applications such as low light absorption efficiency rapid charge recombination and poor stability of photocatalysts. Here the preparation of efficient noble metal–semiconductor hybrid photocatalysts for photocatalytic hydrogen production is presented. The prepared ternary Rh–TiO2–CeO2 hybrid photocatalysts exhibited excellent photocatalytic performance toward the hydrogen production reaction compared with their counterparts ascribed to the synergistic combination of Rh TiO2 and CeO2.
Power-to-fuels Via Solid-oxide Electrolyzer: Operating Window and Techno-economics
May 2019
Publication
Power-to-fuel systems via solid-oxide electrolysis are promising for storing excess renewable electricity by efficient electrolysis of steam (or co-electrolysis of steam and CO2) into hydrogen (or syngas) which can be further converted into synthetic fuels with plant-wise thermal integration. Electrolysis stack performance and durability determine the system design performance and long-term operating strategy; thus solid-oxide electrolyzer based power-to-fuels were investigated from the stack to system levels. At the stack level the data from a 6000-h stack testing under laboratory isothermal conditions were used to calibrate a quasi-2D model which enables to predict practical isothermal stack performance with reasonable accuracy. Feasible stack operating windows meeting various design specifications (e.g. specific syngas composition) were further generated to support the selection of operating points. At the system level with the chosen similar stack operating points various power-to-fuel systems including power-to-hydrogen power-to-methane power-to-methanol (dimethyl ether) and power-to-gasoline were compared techno-economically considering system-level heat integration. Several operating strategies of the stack were compared to address the increase in stack temperature due to degradation. The modeling results show that the system efficiency for producing H2 methane methanol/dimethyl ether and gasoline decreases sequentially from 94% (power-to-H2) to 64% (power-to-gasoline) based on a higher heating value. Co-electrolysis which allows better heat integration can improve the efficiency of the systems with less exothermic fuel-synthesis processes (e.g. methanol/dimethyl ether) but offers limited advantages for power-to-methane and power-to-gasoline systems. In a likely future scenario where the growing amount of electricity from renewable sources results in increasing periods of a negative electricity price solid oxide electrolyser based power-to-fuel systems are highly suitable for levelling the price fluctuations in an economic way.
Role of the Sulphur Source in the Solvothermal Synthesis of Ag-CdS Photocatalysts: Effects on the Structure and Photoactivity for Hydrogen Production
Dec 2020
Publication
The aim of this work is to study the influence of the sulphur source (elemental sulphur thiourea and L-cysteine) in the solvothermal synthesis of Ag-CdS over its growth structuration and state of Ag and how these changes influence on its photoactivity. The differences in the generation rate of the S2− from the sulphur sources during the solvothermal synthesis determine the nucleation and growth pathways of CdS affecting to the silver state and its incorporation into the CdS lattice. The hydrogen production on Ag-CdS photocatalysts decreases according the sequence: thiourea > elemental sulphur >> L-cysteine. The changes in the photoactivity of Ag-CdS samples are analysed in terms of the differences in the insertion of Ag+ into the CdS lattice the formation of composites between CdS and Ag2S and the formation of CdS crystalline domains with strong confinement effect derived from the different sulphur source used in the solvothermal synthesis
Energy Optimization of a Sulfur-Iodine Thermochemical Nuclear Hydrogen Production Cycle
Dec 2021
Publication
The use of nuclear reactors is a large studied possible solution for thermochemical water splitting cycles. Nevertheless there are several problems that have to be solved. One of them is to increase the efficiency of the cycles. Hence in this paper a thermal energy optimization of a SulfureIodine nuclear hydrogen production cycle was performed by means a heuristic method with the aim of minimizing the energy targets of the heat exchanger network at different minimum temperature differences. With this method four different heat exchanger networks are proposed. A reduction of the energy requirements for cooling ranges between 58.9-59.8% and 52.6-53.3% heating compared to the reference design with no heat exchanger network. With this reduction the thermal efficiency of the cycle increased in about 10% in average compared to the reference efficiency. This improves the use of thermal energy of the cycle.
Studies of the Impact of Hydrogen on the Stability of Gaseous Mixtures of THT
Dec 2020
Publication
One of the most important requirements concerning the quality of natural gases guaranteeing their safe use involves providing the proper level of their odorization. This allows for the detection of uncontrolled leakages of gases from gas networks installations and devices. The concentration of an odorant should be adjusted in such a manner that the gas odor in a mixture with air would be noticeable by users (gas receivers). A permanent odor of gas is guaranteed by the stability of the odorant molecule and its resistance to changes in the composition of odorized gases. The article presents the results of experimental research on the impact of a hydrogen additive on the stability of tetrahydrothiophene (THT) mixtures in methane and in natural gas with a hydrogen additive. The objective of the work was to determine the readiness of measurement infrastructures routinely used in monitoring the process of odorizing natural gas for potential changes in its composition. One of the elements of this infrastructure includes the reference mixtures of THT used to verify the correctness of the readings of measurement devices. The performed experimental tests address possible changes in the composition of gases supplied via a distribution network resulting from the introduction of hydrogen. The lack of interaction between hydrogen and THT has been verified indirectly by assessing the stability of its mixtures with methane and natural gas containing hydrogen. The results of the presented tests permitted the identification of potential hazards for the safe use of gas from a distribution network resulting from changes in its composition caused by the addition of hydrogen.
Electrified Hydrogen Production from Methane for PEM Fuel Cells Feeding: A Review
May 2022
Publication
The greatest challenge of our times is to identify low cost and environmentally friendly alternative energy sources to fossil fuels. From this point of view the decarbonization of industrial chemical processes is fundamental and the use of hydrogen as an energy vector usable by fuel cells is strategic. It is possible to tackle the decarbonization of industrial chemical processes with the electrification of systems. The purpose of this review is to provide an overview of the latest research on the electrification of endothermic industrial chemical processes aimed at the production of H2 from methane and its use for energy production through proton exchange membrane fuel cells (PEMFC). In particular two main electrification methods are examined microwave heating (MW) and resistive heating (Joule) aimed at transferring heat directly on the surface of the catalyst. For cases the catalyst formulation and reactor configuration were analyzed and compared. The key aspects of the use of H2 through PEM were also analyzed highlighting the most used catalysts and their performance. With the information contained in this review we want to give scientists and researchers the opportunity to compare both in terms of reactor and energy efficiency the different solutions proposed for the electrification of chemical processes available in the recent literature. In particular through this review it is possible to identify the solutions that allow a possible scale-up of the electrified chemical process imagining a distributed production of hydrogen and its consequent use with PEMs. As for PEMs in the review it is possible to find interesting alternative solutions to platinum with the PGM (Platinum Group Metal) free-based catalysts proposing the use of Fe or Co for PEM application.
The Influence of Hydrogen Sulfide Contaminations on Hydrogen Production in Chemical Looping Processes
Aug 2021
Publication
Chemical looping with iron-based oxygen carriers enables the production of hydrogen from various fossil and biogenic primary energy sources. In applications with real producer gases such as biogas or gasified biomass hydrogen sulfide represents one of the most challenging contaminants. The impact of H2S on the reactivity of a Fe2O3/Al2O3 oxygen carrier material in chemical looping hydrogen production was investigated in the present work. First potential sulfur deactivation mechanisms are discussed in detail on the basis of thermodynamic data. Afterwards an experimental study in a fixed-bed reactor system gave experimental evidence on the fate of sulfur in chemical looping hydrogen systems. The chemisorption of hydrogen sulfide (H2S) was identified as the main cause for the accumulative adsorption of H2S in the reduction phase and was confirmed by ex-situ ICP-EOS analysis. In the subsequent steam oxidation step significant quantities of H2S were released resulting in an undesirable contamination of the hydrogen product gas. The reason was found as weakened sulfur bonds through increasing reactor temperatures caused by the exothermic oxidation reactions. In additional air oxidation steps no further contaminants as sulfur dioxide were identified. A profound interpretation was achieved through the fulfillment of the overall sulfur mass balance within a mean deviation of 3.7%. Quantitative investigations showed that the hydrogen consumption decreased by 12% throughout the reduction phase in the event of 100 ppm H2S in the feed gas
Solar Thermochemical Hydrogen Production in the USA
Jul 2021
Publication
Hydrogen produced from renewable energy has the potential to decarbonize parts of the transport sector and many other industries. For a sustainable replacement of fossil energy carriers both the environmental and economic performance of its production are important. Here the solar thermochemical hydrogen pathway is characterized with a techno-economic and life-cycle analysis. Assuming a further increase of conversion efficiency and a reduction of investment costs it is found that hydrogen can be produced in the United States of America at costs of 2.1–3.2 EUR/kg (2.4–3.6 USD/kg) at specific greenhouse gas emissions of 1.4 kg CO2-eq/kg. A geographical potential analysis shows that a maximum of 8.4 × 1011 kg per year can be produced which corresponds to about twelve times the current global and about 80 times the current US hydrogen production. The best locations are found in the Southwest of the US which have a high solar irradiation and short distances to the sea which is beneficial for access to desalinated water. Unlike for petrochemical products the transport of hydrogen could potentially present an obstacle in terms of cost and emissions under unfavorable circumstances. Given a large-scale deployment low-cost transport seems however feasible.
FPGA-Based Implementation of an Optimization Algorithm to Maximize the Productivity of a Microbial Electrolysis Cell
Jun 2021
Publication
In this work the design of the hardware architecture to implement an algorithm for optimizing the Hydrogen Productivity Rate (HPR) in a Microbial Electrolysis Cell (MEC) is presented. The HPR in the MEC is maximized by the golden section search algorithm in conjunction with a super-twisting controller. The development of the digital architecture in the implementation step of the optimization algorithm was developed in the Very High Description Language (VHDL) and synthesized in a Field Programmable Gate Array (FPGA). Numerical simulations demonstrated the feasibility of the proposed optimization strategy embedded in an FPGA Cyclone II. Results showed that only.
Hollow Cobalt Sulfide Nanocapsules for Electrocatalytic Selective Transfer Hydrogenation of Cinnamaldehyde with Water
Feb 2021
Publication
Designing nanostructured electrocatalysts for selective transfer hydrogenation of α β-unsaturated aldehydes with water as the hydrogen source is highly desirable. Here a facile self-templating strategy is designed for the synthesis of CoS2 and CoS2-x nanocapsules (NCs) as efficient cathodes for selective transfer hydrogenation of cinnamaldehyde a model α β-unsaturated aldehyde. The hollow porous structures of NCs are rich in active sites and improve mass transfer resulting in high turnover frequency. The specific adsorption of the styryl block on pristine CoS2 NCs is conducive to the selective formation of half-hydrogenated hydrocinnamaldehyde with 91.7% selectivity and the preferential adsorption of the C = O group induced by sulfur vacancies on defective CoS2-x NCs leads to the full-hydrogenated hydrocinnamyl alcohol with 92.1% selectivity. A cross-coupling of carbon and hydrogen radicals may be involved in this electrochemical hydrogenation reaction. Furthermore this selective hydrogenation method is also effective for other α β-unsaturated aldehydes illustrating the universality of the method.
Recent Advances in Seawater Electrolysis
Jan 2022
Publication
Hydrogen energy as a clean and renewable energy has attracted much attention in recent years. Water electrolysis via the hydrogen evolution reaction at the cathode coupled with the oxygen evolution reaction at the anode is a promising method to produce hydrogen. Given the shortage of freshwater resources on the planet the direct use of seawater as an electrolyte for hydrogen production has become a hot research topic. Direct use of seawater as the electrolyte for water electrolysis can reduce the cost of hydrogen production due to the great abundance and wide availability. In recent years various high-efficiency electrocatalysts have made great progress in seawater splitting and have shown great potential. This review introduces the mechanisms and challenges of seawater splitting and summarizes the recent progress of various electrocatalysts used for hydrogen and oxygen evolution reaction in seawater electrolysis in recent years. Finally the challenges and future opportunities of seawater electrolysis for hydrogen and oxygen production are presented.
Enhanced Hydrogen Generation from Hydrolysis of MgLi Doped with Expanded Graphite
Apr 2021
Publication
Hydrolysis of Mg-based materials is considered as a potential means of safe and convenient real-time control of H2 release enabling efficient loading discharge and utilization of hydrogen in portable electronic devices. At present work the hydrogen generation properties of MgLi-graphite composites were evaluated for the first time. The MgLi-graphite composites with different doping amounts of expanded graphite (abbreviated as EG hereinafter) were synthesized through ball milling and the hydrogen behaviors of the composites were investigated in chloride solutions. Among the above doping systems the 10 wt% EG-doped MgLi exhibited the best hydrogen performance in MgCl2 solutions. In particular the 22 h-milled MgLi-10 wt% EG composites possessed both desirable hydrogen conversion and rapid reaction kinetics delivering a hydrogen yield of 966 mL H2 g−1 within merely 2 min and a maximum hydrogen generation rate of 1147 mL H2 min−1 g−1 as opposed to the sluggish kinetics in the EG-free composites. Moreover the EG-doped MgLi showed superior air-stable ability even under a 75 RH% ambient atmosphere. For example the 22 h-milled MgLi-10 wt% EG composites held a fuel conversion of 89% after air exposure for 72 h rendering it an advantage for Mg-based materials to safely store and transfer in practical applications. The similar favorable hydrogen performance of MgLi-EG composites in (simulate) seawater may shed light on future development of hydrogen generation technologies.
Towards the Hydrogen Economy—A Review of the Parameters That Influence the Efficiency of Alkaline Water Electrolyzers
May 2021
Publication
Environmental issues make the quest for better and cleaner energy sources a priority. Worldwide researchers and companies are continuously working on this matter taking one of two approaches: either finding new energy sources or improving the efficiency of existing ones. Hydrogen is a well-known energy carrier due to its high energy content but a somewhat elusive one for being a gas with low molecular weight. This review examines the current electrolysis processes for obtaining hydrogen with an emphasis on alkaline water electrolysis. This process is far from being new but research shows that there is still plenty of room for improvement. The efficiency of an electrolyzer mainly relates to the overpotential and resistances in the cell. This work shows that the path to better electrolyzer efficiency is through the optimization of the cell components and operating conditions. Following a brief introduction to the thermodynamics and kinetics of water electrolysis the most recent developments on several parameters (e.g. electrocatalysts electrolyte composition separator interelectrode distance) are highlighted.
Thermodynamic Analysis of Hydrogen Production via Chemical Looping Steam Methane Reforming Coupled with In Situ CO2 Capture
Dec 2014
Publication
A detailed thermodynamic analysis of the sorption enhanced chemical looping reforming of methane (SE-CL-SMR) using CaO and NiO as CO2 sorbent and oxygen transfer material (OTM) respectively was conducted. Conventional reforming (SMR) and sorption enhanced reforming (SE-SMR) were also investigated for comparison reasons. The results of the thermodynamic analysis show that there are significant advantages of both sorption enhanced processes compared to conventional reforming. The presence of CaO leads to higher methane conversion and hydrogen purity at low temperatures. Addition of the OTM in the SECL-SMR process concept minimizes the thermal requirements and results in superior performance compared to SE-SMR and SMR in a two-reactor concept with use of pure oxygen as oxidant/sweep gas.
Integration of a Dark Fermentation Effluent in a Microalgal-based Biorefinery for the Production of High-added Value Omega-3 Fatty Acids
Mar 2019
Publication
Dark fermentation is an anaerobic digestion process of biowaste used to produce hydrogen- for generation of energy- that however releases high amounts of polluting volatile fatty acids such as acetic acid in the environment. In order for this biohydrogen production process to become more competitive the volatile fatty acids stream can be utilized through conversion to high added-value metabolites such as omega-3 fatty acids. The docosahexaenoic acid is one of the two most known omega-3 fatty acids and has been found to be necessary for a healthy brain and proper cardiovascular function. The main source is currently fish which obtain the fatty acid from the primary producers microalgae through the food chain. Crypthecodinium cohnii a heterotrophic marine microalga is known for accumulating high amounts of docosahexaenoic acid while offering the advantage of assimilating various carbon sources such as glucose ethanol glycerol and acetic acid. The purpose of this work was to examine the ability of a C. cohnii strain to grow on different volatile fatty acids as well as on a pre-treated dark fermentation effluent and accumulate omega-3. The strain was found to grow well on relatively high concentrations of acetic butyric or propionic acid as main carbon source in a fed-batch pH-auxostat. Most importantly C. cohnii totally depleted the organic acid content of an ultra-filtrated dark fermentation effluent after 60 h of fed-batch cultivation therefore offering a bioprocess not only able to mitigate environmental pollutants but also to provide a solution for a sustainable energy production process. The accumulated docosahexaenoic acid content was as high as 29.8% (w/w) of total fatty acids.
Molybdenum Carbide Microcrystals: Efficient and Stable Catalyst for Photocatalytic H2 Evolution From Water in The Presence Of Dye Sensitizer
Sep 2016
Publication
Rod-like molybdenum carbide (Mo2C) microcrystals were obtained from the pyrolysis of Mo-containing organic-inorganic hybrid composite. We investigated the photocatalytic H2 evolution activity of Mo2C by constructing a Mo2C-dye sensitizer photocatalyst system. A high quantum efficiency of 29.7% was obtained at 480 nm. Moreover Mo2C catalyst can be easily recycled by simple filtration.
Raw Biomass Electroreforming Coupled to Green Hydrogen Generation
Mar 2021
Publication
Despite the tremendous progress of coupling organic electrooxidation with hydrogen generation in a hybrid electrolysis electroreforming of raw biomass coupled to green hydrogen generation has not been reported yet due to the rigid polymeric structures of raw biomass. Herein we electrooxidize the most abundant natural amino biopolymer chitin to acetate with over 90% yield in hybrid electrolysis. The overall energy consumption of electrolysis can be reduced by 15% due to the thermodynamically and kinetically more favorable chitin oxidation over water oxidation. In obvious contrast to small organics as the anodic reactant the abundance of chitin endows the new oxidation reaction excellent scalability. A solar-driven electroreforming of chitin and chitin-containing shrimp shell waste is coupled to safe green hydrogen production thanks to the liquid anodic product and suppression of oxygen evolution. Our work thus demonstrates a scalable and safe process for resource upcycling and green hydrogen production for a sustainable energy future.
Methane Emissions from Natural Gas and LNG Imports: An Increasingly Urgent Issue for the Future of Gas in Europe
Nov 2020
Publication
Pressure is mounting on the natural gas and LNG community to reduce methane emissions and this is most urgent in EU countries following the adoption of much tougher greenhouse gas reduction targets of 2030 and the publication of the European Commission’s Methane Strategy. With rapidly declining indigenous EU production and therefore rising import dependence there are increasing calls for emissions from imported pipeline gas and LNG to be quantified and based on actual measurements as opposed to standard emission factors. The Methane Strategy promises to be a significant milestone in that process. Companies which are supplying (or intending to supply) natural gas to the EU – the largest global import market for pipeline gas and a very significant market for LNG – would be well advised to pay close attention to how the regulation of methane emissions is unfolding and to make an immediate and positive response. Failure to do so could accelerate the demise of natural gas in European energy balances faster than would otherwise have been the case and shorten the time available for transition to decarbonised gases – specifically hydrogen – using existing natural gas infrastructure.<br/>This EU initiative will (and arguably already has) attracted attention from non-EU governments and companies involved in global gas and LNG trade. We have already seen deliveries of `carbon neutral’ LNG cargos to Asia as well as a long-term LNG contract in which the greenhouse gas content of cargos will be measured reported and verified (MRV) according to an agreed methodology. Natural gas and LNG exports if based on these standards or those set out in the EU Methane Strategy may be able to command premium prices from buyers eager to demonstrate their own GHG reduction credentials to governments customers and civil society.
Heat to Hydrogen by RED—Reviewing Membranes and Salts for the RED Heat Engine Concept
Dec 2021
Publication
The Reverse electrodialysis heat engine (REDHE) combines a reverse electrodialysis stack for power generation with a thermal regeneration unit to restore the concentration difference of the salt solutions. Current approaches for converting low-temperature waste heat to electricity with REDHE have not yielded conversion efficiencies and profits that would allow for the industrialization of the technology. This review explores the concept of Heat-to-Hydrogen with REDHEs and maps crucial developments toward industrialization. We discuss current advances in membrane development that are vital for the breakthrough of the RED Heat Engine. In addition the choice of salt is a crucial factor that has not received enough attention in the field. Based on ion properties relevant for both the transport through IEMs and the feasibility for regeneration we pinpoint the most promising salts for use in REDHE which we find to be KNO3 LiNO3 LiBr and LiCl. To further validate these results and compare the system performance with different salts there is a demand for a comprehensive thermodynamic model of the REDHE that considers all its units. Guided by such a model experimental studies can be designed to utilize the most favorable process conditions (e.g. salt solutions).
Control of Electrons’ Spin Eliminates Hydrogen Peroxide Formation During Water Splitting
Jul 2017
Publication
The production of hydrogen through water splitting in a photoelectrochemical cell suffers from an overpotential that limits the efficiencies. In addition hydrogen-peroxide formation is identified as a competing process affecting the oxidative stability of photoelectrodes. We impose spin-selectivity by coating the anode with chiral organic semiconductors from helically aggregated dyes as sensitizers; Zn-porphyrins and triarylamines. Hydrogen peroxide formation is dramatically suppressed while the overall current through the cell correlating with the water splitting process is enhanced. Evidence for a strong spin-selection in the chiral semiconductors is presented by magnetic conducting (mc-)AFM measurements in which chiral and achiral Zn-porphyrins are compared. These findings contribute to our understanding of the underlying mechanism of spin selectivity in multiple electron-transfer reactions and pave the way toward better chiral dye-sensitized photoelectrochemical cells.
H2 Green Hydrogen Discussion Paper: Victorian Hydrogen Investment Program
Nov 2019
Publication
This discussion paper is for stakeholders who would like to shape the development of Victoria’s emerging green hydrogen sector identifying competitive advantages and priority focus areas for industry and the Victorian Government.<br/>The Victorian Government is using this paper to focus on the economic growth and sector development opportunities emerging for a Victorian hydrogen industry powered by renewable energy also known as ‘green’ hydrogen. In addition this paper seeks input from all stakeholders on how where and when the Victorian Government can act to establish a thriving green hydrogen economy.<br/>Although green hydrogen is the only type of hydrogen production within the scope of this discussion paper the development of the VHIP aligns with the policies projects and initiatives which support these other forms of hydrogen production. The VHIP is considering the broad policy landscape and actively coordinating with related hydrogen programs policies and strategies under development including the Council of Australian Governments (COAG) Energy Council’s National Hydrogen Strategy to ensure a complementary approach. In Victoria there are several programs and strategies in development and underway that have linkages with hydrogen and the VHIP.
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