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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.

Hydrogen (H₂) shows promise as an energy carrier in contributing to emissions reductions from sectors which have been difficult to decarbonize like industry and transportation. At the same time flexible H₂ production via electrolysis can also support cost-effective integration of high shares of variable renewable energy (VRE) in the power system. In this work we develop a least-cost investment planning model to co-optimize investments in electricity and H₂ infrastructure to serve electricity and H₂ demands under various low-carbon scenarios. Applying the model to a case study of Texas in 2050 we find that H2 is produced in approximately equal amounts from electricity and natural gas under the least-cost expansion plan with a CO₂ price of $30–60/tonne. An increasing CO₂ price favors electrolysis while increasing H2 demand favors H₂ production from Steam Methane Reforming (SMR) of natural gas. H₂ production is found to be a cost effective solution to reduce emissions in the electric power system as it provides flexibility otherwise provided by natural gas power plants and enables high shares of VRE with less battery storage. Additionally the availability of flexible electricity demand via electrolysis makes carbon capture and storage (CCS) deployment for SMR cost-effective at lower CO₂ prices ($90/tonne CO₂) than for power generation ($180/tonne CO₂ ). The total emissions attributable to H₂ production is found to be dependent on the H2 demand. The marginal emissions from H₂ production increase with the H₂ demand for CO₂ prices less than $90/tonne CO₂  due to shift in supply from electrolysis to SMR. For a CO₂ price of $60/tonne we estimate the production weighted-average H₂ price to be between $1.30–1.66/kg across three H₂ demand scenarios. These findings indicate the importance of joint planning of electricity and H2 infrastructure for cost-effective energy system decarbonization.

This paper proposes an integration of concentrating solar power (CSP) with a sorption-enhanced steam methane reforming (SE-SMR) process and assesses its overall solar-to-fuel conversion performance. A thermodynamic treatment of the SE-SMR process for H2 production is presented and evaluated in an innovative two reactors system configuration using CSP as a heat input. Four metal carbonate/metal oxide pairs are considered and the equilibrium thermodynamics reveals that CaCO3/CaO pair is the most suitable candidate for this process. Additionally a reactor-scale thermodynamic model is developed to determine the optimum operating conditions for the process. For the carbonation step temperatures between 700 and 900 K and steam-to-methane ratio ≥4 are found to be the most favorable. Furthermore an advanced process model which utilizes operating conditions determined from the reactor-scale model is developed to evaluate the process efficiency. The model predicts that the proposed process can achieve a solar-to-fuel efficiency ~41% for calcination temperature of 1500 K and carbonation temperature of 800 K without considering any solid heat recovery. An additional 2.5% increase in the process efficiency is feasible with the consideration of the solid heat recovery. This study shows the thermodynamic feasibility of integrating the SE-SMR process with CSP technologies.

Interactions between incident electromagnetic energy and matter are of critical importance for numerous civil and military applications such as photocatalysis solar cells optics radar detection communications information processing and transport et al. Traditional mechanisms for such interactions in the microwave frequency mainly rely on dipole rotations and magnetic domain resonance. In this study we present the first report of the microwave absorption of Al/H₂ treated TiO₂ nanoparticles where the Al/H₂ treatment not only induces structural and optical property changes but also largely improves the microwave absorption performance of TiO₂ nanoparticles. Moreover the frequency of the microwave absorption can be finely controlled with the treatment temperature and the absorption efficiency can reach optimal values with a careful temperature tuning. A large reflection loss of −58.02 dB has been demonstrated with 3.1 mm TiO₂ coating when the treating temperature is 700 °C. The high efficiency of microwave absorption is most likely linked to the disordering-induced property changes in the materials. Along with the increased microwave absorption properties are largely increased visible-light and IR absorptions and enhanced electrical conductivity and reduced skin-depth which is likely related to the interfacial defects within the TiO₂ nanoparticles caused by the Al/H₂ treatment.

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.

Managing the concentration of atmospheric CO₂ requires a multifaceted engineering strategy which remains a highly challenging task. Reducing atmospheric CO₂ (CO2R) by converting it to value-added chemicals in a carbon neutral footprint manner must be the ultimate goal. The latest progress in CO2R through either abiotic (artificial catalysts) or biotic (natural enzymes) processes is reviewed herein. Abiotic CO2R can be conducted in the aqueous phase that usually leads to the formation of a mixture of CO formic acid and hydrogen. By contrast a wide spectrum of hydrocarbon species is often observed by abiotic CO2R in the gaseous phase. On the other hand biotic CO2R is often conducted in the aqueous phase and a wide spectrum of value-added chemicals are obtained. Key to the success of the abiotic process is understanding the surface chemistry of catalysts which significantly governs the reactivity and selectivity of CO2R. However in biotic CO2R operation conditions and reactor design are crucial to reaching a neutral carbon footprint. Future research needs to look toward neutral or even negative carbon footprint CO2R processes. Having a deep insight into the scientific and technological aspect of both abiotic and biotic CO2R would advance in designing efficient catalysts and microalgae farming systems. Integrating the abiotic and biotic CO2R such as microbial fuel cells further diversifies the spectrum of CO2R.

A new assessment tool for evaluating decarbonization technologies that considers each technology’s sustainability security affordability readiness and impact for a specific country is proposed. This tool is applied to a set of decarbonization technologies for the power transport and industry sectors for the ten Southeast Asian countries that constitute ASEAN. This results in a list of the most promising decarbonization technologies as well as the remaining issues that need more research and development. This study reveals several common themes for ASEAN’s decarbonization. First carbon capture and storage (CCS) is a key technology for large-scale CO2 emission. Second for countries that rely heavily on coal for power generation switching to gas can halve their CO2 emission in the power sector and should be given high priority. Third hydropower and bioenergy both have high potential for the majority of ASEAN countries if their sustainability issues can be resolved satisfactorily. Fourth replacing conventional vehicles by electric vehicles is the overarching theme in the road transport sector but will result in increased demand for electricity. In the medium to long term the use of hydrogen for marine fuel and biofuels for aviation fuel are preferred solutions for the marine and aviation transport sectors. Fifth for the industry sector installing CCS in industrial plants should be given priority but replacing fossil fuels by blue hydrogen for high-temperature heating is the preferred long-term solution.

Proton conducting SmNiO₃ (SNO) thin films were grown on (001) LaAlO₃ substrates for systematically investigating the proton transport properties. X-ray Diffraction and Atomic Force Microscopy studies reveal that the as-grown SNO thin films have good single crystallinity and smooth surface morphology. The electrical conductivity measurements in air indicate a peak at 473 K in the temperature dependence of the resistance of the SNO films probably due to oxygen loss on heating. A Metal-Insulator-Transition occurs at 373 K for the films after annealing at 873 K in air. In a hydrogen atmosphere (3% H2/97% N₂) an anomalous peak in the resistance is found at 685 K on the first heating cycle. Electrochemical Impedance Spectroscopy studies as a function of temperature indicate that the SNO films have a high ionic conductivity (0.030 S/cm at 773 K) in a hydrogen atmosphere. The activation energy for proton conductivity was determined to be 0.23 eV at 473–773 K and 0.37 eV at 773–973 K respectively. These findings demonstrate that SNO thin films have good proton conductivity and are good candidate electrolytes for low temperature proton-conducting Solid Oxide Fuel Cells.

In the search for new efficient photo-catalysts for hydrogen production through water splitting the main attention has been paid to tuning the band gap width and its position with respect to vacuum level. However actual electro-catalytic activity for the water oxidation reaction on a catalyst surface is no less important than those quantities. In this work we evaluate from first principles the thermodynamics of the reaction on relatively new candidates for water splitting: two-dimensional C₂N and that doped with phosphorus. We find that the 4-step reaction usually expected for water splitting will not proceed on these systems resulting in oxygen atoms left strongly adsorbed to the surface. Another option a 3-step reaction is also found to be unfavorable. We also test an effect of higher oxygen coverage on the reaction thermodynamics as suggested elsewhere. We find that indeed the doubled O-coverage makes the 4-step reaction feasible for the doped C₂N. However an unacceptably high anode potential is required to make this reaction proceed. We thus conclude that the materials under consideration may not be efficient electro-catalysts for water splitting.

The Pd-H system has attracted extensive attention. Pd can absorb considerable amount of H at room temperature this ability is reversible so it is suitable for multiple energy applications. Pd-Ag alloys possess higher H permeability solubility and narrower miscibility gap with better mechanical properties than pure Pd but sulfur poisoning remains an issue. Pd-Cu alloys have excellent resistance to sulfur and carbon monoxide poisoning and hydrogen embrittlement good mechanical properties and broader temperature working environments over pure Pd but relatively lower hydrogen permeability and solubility than pure Pd and Pd-Ag alloys. This suggests that alloying Pd with Ag and Cu to create Pd-Ag-Cu ternary alloys can optimize the overall performance and substantially lowers the cost. Thus in this paper we provide the first embedded atom method potentials for the quaternary hydrides Pd_1-y-zAgyCu_zH_x. The fully analytical potentials are fitted utilizing the central atom method without performing time-consuming molecular dynamics simulations.

The protonic ceramic electrochemical cell (PCEC) is an emerging and attractive technology that converts energy between power and hydrogen using solid oxide proton conductors at intermediate temperatures. To achieve efficient electrochemical hydrogen and power production with stable operation highly robust and durable electrodes are urgently desired to facilitate water oxidation and oxygen reduction reactions which are the critical steps for both electrolysis and fuel cell operation especially at reduced temperatures. In this study a triple conducting oxide of PrNi0.5Co0.5O3-δ perovskite is developed as an oxygen electrode presenting superior electrochemical performance at 400~600 °C. More importantly the self-sustainable and reversible operation is successfully demonstrated by converting the generated hydrogen in electrolysis mode to electricity without any hydrogen addition. The excellent electrocatalytic activity is attributed to the considerable proton conduction as confirmed by hydrogen permeation experiment remarkable hydration behavior and computations.

Several manufacturers are developing heavy duty (HD) hydrogen stations and vehicles as zeroemissions alternatives to diesel and gasoline. In order to meet customer demands the new technology must be comparable to conventional approaches including safety reliability fueling times and final fill levels. For a large HD vehicle with a storage rated to 70 MPa nominal working pressure the goal to meet liquid fuel parity means providing 100 kg of hydrogen in 10 minutes. This paper summarizes the results to date of the PRHYDE project efforts to define the concepts of HD fueling which thereby lays the groundwork for the development of the safe and effective approach to filling these large vehicles. The project starts by evaluating the impact of several different assumptions such as the availability of static vehicle data (e.g. vehicle tank type and volume) and station data (e.g. expected station precooling capability) but also considers using real time dynamic data (e.g. vehicle tank gas temperature and pressure station gas temperature etc.) for optimisation to achieve safety and efficiency improvements. With this information the vehicle or station can develop multiple maps of fill time versus the hydrogen delivery temperature which are used to determine the speed of fueling. This will also allow the station or vehicle to adjust the rate of fueling as the station pre-cooling levels and other conditions change. The project also examines different steps for future protocol development such as communication of data between the vehicle and station and if the vehicle or station is controlling the fueling.

A better understanding of chemical kinetics under volumetric expansion is important for a number of situations relevant to industrial safety including detonation diffraction and direct initiation reflected shock-ignition at obstacles ignition behind a decaying shock among others. The ignition of stoichiometric hydrogen-air mixtures was studied using 0D numerical simulations with time-dependent specific volume variations. The competition between chemical energy release and expansion-induced cooling was characterized for different cooling rates and mathematical forms describing the shock decay rate. The critical conditions for reaction quenching were systematically determined and the thermo-chemistry dynamics were analyzed near the critical conditions.

Austenitic stainless steels are used for hydrogen containment of high-pressure hydrogen gas due to their ability to retain high fracture properties despite the degradation due to hydrogen. Forging and other strain-hardening processes are desirable for austenitic stainless steels to increase the material strength and thus accommodate higher stresses and reduce material costs. Welding is often necessary for assembling components but it represents an area of concern in pressure containment structures due to the potential for defects more environmentally susceptible microstructure and reduced strength. Electron beam (EB) welding represent an advanced joining process which has advantages over traditional arc welding techniques through reduced input heat and reduced heat-affected zone (HAZ) microstructure and thus present a means to maintain high strength and improve weld performance in hydrogen gas containment. In this study fracture coupons were extracted from EB welds in forged 304L and subjected to thermal gaseous hydrogen precharging at select pressures to introduce different levels of internal hydrogen content. Fracture tests were then performed on hydrogen precharged coupons at temperatures of both 293 K and 223 K. It was observed that fracture resistance (JH) was dependent on internal hydrogen concentration; higher hydrogen concentrations resulted in lower fracture resistance in both the forged 304L base material and the 304L EB welds. This trend was also apparent at both temperatures: 293 K and 223 K. EB weld samples however maintain high fracture resistance comparable to the forged 304L base material. The role of weld microstructure solidification on fracture is discussed.

In this paper we report the effect of adding Zr + V or Zr + V + Mn to TiFe alloy on microstructure and hydrogen storage properties. The addition of only V was not enough to produce a minimum amount of secondary phase and therefore the first hydrogenation at room temperature under a hydrogen pressure of 20 bars was impossible. When 2 wt.% Zr + 2 wt.% V or 2 wt.% Zr + 2 wt.% V + 2 wt.% Mn is added to TiFe the alloy shows a finely distributed Ti₂Fe-like secondary phase. These alloys presented a fast first hydrogenation and a high capacity. The rate-limiting step was found to be 3D growth diffusion controlled with decreasing interface velocity. This is consistent with the hypothesis that the fast reaction is likely to be the presence of Ti₂Fe-like secondary phases that act as a gateway for hydrogen.

Photoelectrochemical (PEC) water splitting is a promising technology for solar hydrogen production to build a sustainable renewable and clean energy economy. Given the complexity of the PEC water splitting processes it is important to note that developing in-situ techniques for studying PEC water splitting presents a formidable challenge. This review is aimed at highlighting advantages and disadvantages of each technique while offering a pathway of potentially combining several techniques to address different aspects of interfacial processes in PEC water splitting. We reviewed recent progress in various techniques and approaches utilized to study PEC water splitting focusing on spectroscopic and scanning-probe methods.

The European Community requires a vehicle-level bonfire test for vehicles using plastic fuel tanks for conventional fuels (ECE R-34 Annex 5). A similar test could be applied to hydrogen-fuelled vehicles. It would test a realistic vehicle with its complete fuel and safety systems. An advantage of such a test is that the same test could be applied independent of the hydrogen storage technology (compressed gas liquid or hydride). There are currently standards for bonfire testing of a bare Compressed Natural Gas (CNG) tank and its Pressure Relief Device (PRD). This standard is FMVSS 304 in the U.S. and ISO 15869-1 in Europe. Japan has a similar standard. It requires that a bare tank and its associated PRD be subjected to a propane flame for 20 minutes. The tank must either survive or safely vent its contents. No modern composite wound tank is expected to survive for 20 minutes – so this is not a tank test but really a PRD test. The test procedure requires the PRD to be shielded from direct impingement of the flames – but the shield is not well specified. If it shields the PRD too well the PRD will not activate and the tank will burst. This paper describes the results of a CNG and a hydrogen tank burst from such tests. The mechanical energy released is enormous. It is simply unacceptable to allow the tank to burst – the PRD and venting system must work. Organizations in the U.S Europe and Japan are in the process of modifying the CNG tank bonfire test for compressed hydrogen storage. A bare tank with a single PRD is not a good simulation of a hydrogen fuel system installed in an actual vehicle. There will usually be multiple tanks plumbed together at either the tank pressure or at the intermediate pressure (after the pressure regulator). There may be more than one PRD. The tank may be shielded (from debris) or insulated to protect it from an underbody pool fire. Also the heat transfer from the simulated pool fire (propane flame) will be very different when mounted in a vehicle versus the bare tank test. A vehicle-level pool fire test will alleviate these problems. It is therefore recommended that the bare tank test be replaced by or augmented with a vehicle-level bonfire test similar to ECE R-34 Annex 5.

Because of their high surface areas crystallinity and tunable propertiesmetal−organic frameworks (MOFs) have attracted intense interest as next-generationmaterials for gas capture and storage. While much effort has been devoted to thediscovery of new MOFs a vast catalog of existing MOFs resides within the CambridgeStructural Database (CSD) many of whose gas uptake properties have not beenassessed. Here we employ data mining and automated structure analysis to identify“cleanup” and rapidly predict the hydrogen storage properties of these compounds.Approximately 20 000 candidate compounds were generated from the CSD using analgorithm that removes solvent/guest molecules. These compounds were thencharacterized with respect to their surface area and porosity. Employing the empiricalrelationship between excess H2 uptake and surface area we predict the theoretical total hydrogen storage capacity for the subsetof ∼4000 compounds exhibiting nontrivial internal porosity. Our screening identifies several overlooked compounds having hightheoretical capacities; these compounds are suggested as targets of opportunity for additional experimental characterization.More importantly screening reveals that the relationship between gravimetric and volumetric H2 density is concave downwardwith maximal volumetric performance occurring for surface areas of 3100−4800 m2 /g. We conclude that H2 storage in MOFswill not benefit from further improvements in surface area alone. Rather discovery efforts should aim to achieve moderate massdensities and surface areas simultaneously while ensuring framework stability upon solvent removal.

Missions targeting the extreme and rugged environments on the moon and Mars have rich potential for a high science return although several risks exist in performing these exploration missions. The current generation of robots is unable to access these high-priority targets. We propose using teams of small hopping and rolling robots called SphereX that are several kilograms in mass and can be carried by a large rover or lander and tactically deployed for exploring these extreme environments. Considering that the importance of minimizing the mass and volume of these robot platforms translates into significant mission-cost savings we focus on the optimization of an integrated power and propulsion system for SphereX. Hydrogen is used as fuel for its high energy and it is stored in the form of lithium hydride and oxygen in the form of lithium perchlorate. The system design undergoes optimization using Genetic Algorithms integrated with gradient-based search techniques to find optimal solutions for a mission. Our power and propulsion system as we show in this paper is enabling because the robots can travel long distances to perform science exploration by accessing targets not possible with conventional systems. Our work includes finding the optimal mass and volume of SphereX such that it can meet end-to-end mission requirements.

A 10-minute tour of hydrogen industry technology and terminology for those who are new to the sector or who would simply like a quick review of the basics behind this burgeoning energy source.

Podcast can be found on their website

The year 2014 marked hydrogen fuel cell electric vehicles (FCEVs) first becoming commercially available in California where significant investments are being made to promote the adoption of alternative transportation fuels. A refueling infrastructure network that guarantees adequate coverage and expands in line with vehicle sales is required for FCEVs to be successfully adopted by private customers. In this paper we provide an overview of modelling methodologies used to project hydrogen refueling infrastructure requirements to support FCEV adoption and we describe in detail the National Renewable Energy Laboratory’s scenario evaluation and regionalization analysis (SERA) model. As an example we use SERA to explore two alternative scenarios of FCEV adoption: one in which FCEV deployment is limited to California and several major cities in the United States; and one in which FCEVs reach widespread adoption becoming a major option as passenger vehicles across the entire country. Such scenarios can provide guidance and insights for efforts required to deploy the infrastructure supporting transition toward different levels of hydrogen use as a transportation fuel for passenger vehicles in the United States.

This paper investigates the optimal planning of microgrids including the hydrogen energy system through mixed-integer linear programming model. A real case study is analyzed by extending the only microgrid lab facility in Austria. The case study considers the hydrogen production via electrolysis seasonal storage and fuelling station for meeting the hydrogen fuel demand of fuel cell vehicles busses and trucks. The optimization is performed relative to two different reference cases which satisfy the mobility demand by diesel fuel and utility electricity based hydrogen fuel production respectively. The key results indicate that the low emission hydrogen mobility framework is achieved by high share of renewable energy sources and seasonal hydrogen storage in the microgrid. The investment optimization scenarios provide at least 66% and at most 99% carbon emission savings at increased costs of 30% and 100% respectively relative to the costs of the diesel reference case (current situation)

Two non-electrified railway lines one in Norway and the other in the USA are analysed for their potential to be electrified with overhead line equipment batteries hydrogen or hydrogen-battery hybrid powertrains. The energy requirements are established with single-train simulations including the altitude profiles of the lines air and rolling resistances and locomotive tractive-effort curves. The composition of the freight trains in terms of the number of locomotives battery wagons hydrogen wagons etc. is also calculated by the same model. The different technologies are compared by the criteria of equivalent annual costs benefit–cost ratio payback period and up-front investment based on the estimated techno-economic parameters for years 2020 2030 and 2050. The results indicate the potential of batteries and fuel cells to replace diesel on rail lines with low traffic volumes.

In this perspective on hydrogen carriers we focus on the needs for the development of robust active catalysts for the release of H₂ from aqueous formate solutions which are non-flammable non-toxic thermally stable and readily available at large scales at reasonable cost. Formate salts can be stockpiled in the solid state or dissolved in water for long term storage and transport using existing infrastructure. Furthermore formate salts are readily regenerated at moderate pressures using the same catalyst as for the H₂ release. There have been several studies focused on increasing the activity of catalysts to release H₂ at moderate temperatures i.e. < 80 °C below the operating temperature of a proton exchange membrane (PEM) fuel cell. One significant challenge to enable the use of aqueous formate salts as hydrogen carriers is the deactivation of the catalyst under operating conditions. In this work we provide a review of the most efficient heterogeneous catalysts that have been described in the literature their proposed modes of deactivation and the strategies reported to reactivate them. We discuss potential pathways that may lead to deactivation and strategies to mitigate it in a variety of H₂ carrier applications. We also provide an example of a potential use case employing formate salts solutions using a fixed bed reactor for seasonal storage of energy for a microgrid application.

Green synthesis of crystalline porous materials for energy-related applications is of great significance but very challenging. Here we create a green strategy to fabricate a highly crystalline olefin-linked pyrazine-based covalent organic framework (COF) with high robustness and porosity under solvent-free conditions. The abundant nitrogen sites high hydrophilicity and well-defined one-dimensional nanochannels make the resulting COF an ideal platform to confine and stabilize the H₃PO₄ network in the pores through hydrogen-bonding interactions. The resulting material exhibits low activation energy (E_a) of 0.06 eV and ultrahigh proton conductivity across a wide relative humidity (10–90 %) and temperature range (25–80 °C). A realistic proton exchange membrane fuel cell using the olefin-linked COF as the solid electrolyte achieve a maximum power of 135 mW cm⁻² and a current density of 676 mA cm⁻² which exceeds all reported COF materials.