China, People’s Republic
Effects of Hot Stamping and Tempering on Hydrogen Embrittlement of a Low-Carbon Boron-Alloyed Steel
Dec 2018
Publication
The effects of hot stamping (HS) and tempering on the hydrogen embrittlement (HE) behavior of a low-carbon boron-alloyed steel were studied by using slow strain rate tensile (SSRT) tests on notched sheet specimens. It was found that an additional significant hydrogen desorption peak at round 65–80 °C appeared after hydrogen-charging the corresponding hydrogen concentration (CHr) of the HS specimen was higher than that of the directed quenched (DQ) specimen and subsequent low-temperature tempering gave rise to a decrease of CHr. The DQ specimen exhibited a comparatively high HE susceptibility while tempering treatment at 100 °C could notably alleviate it by a relative decrease of ~24% at no expanse of strength and ductility. The HS specimen demonstrated much lower HE susceptibility compared with the DQ specimen and tempering at 200 °C could further alleviate its HE susceptibility. SEM analysis of fractured SSRT surfaces revealed that the DQ specimen showed a mixed transgranular-intergranular fracture while the HS and low-temperature tempered specimens exhibited a predominant quasi-cleavage transgranular fracture. Based on the obtained results we propose that a modified HS process coupled with low-temperature tempering treatment is a promising and feasible approach to ensure a low HE susceptibility for high-strength automobile parts made of this type of steel.
Two-dimensional Vanadium Carbide for Simultaneously Tailoring the Hydrogen Sorption Thermodynamics and Kinetics of Magnesium Hydride
May 2021
Publication
Magnesium hydride (MgH2) is a potential material for solid-state hydrogen storage. However the thermodynamic and kinetic properties are far from practical application in the current stage. In this work two-dimensional vanadium carbide (V2C) MXene with layer thickness of 50−100 nm was fist synthesized by selectively HF-etching the Al layers from V2AlC MAX phase and then introduced into MgH2 to improve the hydrogen sorption performances of MgH2. The onset hydrogen desorption temperature of MgH2 with V2C addition is significantly reduced from 318 °C for pure MgH2 to 190 °C with a 128 °C reduction of the onset temperature. The MgH2+ 10 wt% V2C composite can release 6.4 wt% of H2 within 10 min at 300 °C and does not loss any capacity for up to 10 cycles. The activation energy for the hydrogen desorption reaction of MgH2 with V2C addition was calculated to be 112 kJ mol−1 H2 by Arrhenius's equation and 87.6 kJ mol−1 H2 by Kissinger's equation. The hydrogen desorption reaction enthalpy of MgH2 + 10 wt% V2C was estimated by van't Hoff equation to be 73.6 kJ mol−1 H2 which is slightly lower than that of the pure MgH2 (77.9 kJ mol−1 H2). Microstructure studies by XPS TEM and SEM showed that V2C acts as an efficient catalyst for the hydrogen desorption reaction of MgH2. The first-principles density functional theory (DFT) calculations demonstrated that the bond length of Mg−H can be reduced from 1.71 Å for pure MgH2 to 2.14 Å for MgH2 with V2C addition which contributes to the destabilization of MgH2. This work provides a method to significantly and simultaneously tailor the hydrogen sorption thermodynamics and kinetics of MgH2 by two-dimensional MXene materials.
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.
Extreme Energetic Materials at Ultrahigh Pressures
Jul 2020
Publication
Owing to their extremely high energy density single-bonded polymeric nitrogen and atomic metallic hydrogen are generally regarded as the ultimate energetic materials. Although their syntheses normally require ultrahigh pressures of several hundred gigapascals (GPa) which prohibit direct materials application research on their stability metastability and fundamental properties are valuable for seeking extreme energetic materials through alternative synthetic routes. Various crystalline and amorphous polymeric nitrogens have been discovered between 100 and 200 GPa. Metastability at ambient conditions has been demonstrated for some of these phases. Cubic-gauche and black-phosphorus polymorphs of single-bonded nitrogen are two particularly interesting phases. Their large hystereses warrant further application-inspired basic research of nitrogen. In contrast although metallic hydrogen contains the highest-estimated energy density its picosecond lifetime and picogram quantity make its practical material application impossible at present. “Metallic hydrogen” remains a curiosity-driven basic research pursuit focusing on the pressure-induced evolution of the molecular hydrogen crystal and its electronic band structure from a low-density insulator with a very wide electronic band gap to a semiconductor with a narrow gap to a dense molecular metal and atomic metal and eventually to a previously unknown exotic state of matter. This great experimental challenge is driving relentless advancement in ultrahigh-pressure science and technology.
Towards Global Cleaner Energy and Hydrogen Production: A Review and Application ORC Integrality with Multigeneration Systems
Apr 2022
Publication
The current evidential effect of carbon emissions has become a societal challenge and the need to transition to cleaner energy sources/technologies has attracted wide research attention. Technologies that utilize low-grade heat like the organic Rankine cycle (ORC) and Kalina cycle have been proposed as viable approaches for fossil reduction/carbon mitigation. The development of renewable energy-based multigeneration systems is another alternative solution to this global challenge. Hence it is important to monitor the development of multigeneration energy systems based on low-grade heat. In this study a review of the ORC’s application in multigeneration systems is presented to highlight the recent development in ORC integrality/application. Beyond this a new ORC-CPVT (concentrated photovoltaic/thermal) integrated multigeneration system is also modeled and analyzed using the thermodynamics approach. Since most CPVT systems integrate hot water production in the thermal stem the proposed multigeneration system is designed to utilize part of the thermal energy to generate electricity and hydrogen. Although the CPVT system can achieve high energetic and exergetic efficiencies while producing thermal energy and electricity these efficiencies are 47.9% and 37.88% respectively for the CPVT-ORC multigeneration configuration. However it is noteworthy that the electricity generation from the CPVT-ORC configuration in this study is increased by 16%. In addition the hot water cooling effect and hydrogen generated from the multigeneration system are 0.4363 L/s 161 kW and 1.515 L/s respectively. The environmental analysis of the system also shows that the carbon emissions reduction potential is enormous.
Construction of Natural Gas Energy-measuring System in China: A Discussion
Feb 2022
Publication
During the 13th Five-Year Plan China's natural gas industry developed rapidly and a diversified supply and marketing pattern was formed including domestic conventional gas unconventional gas (shale gas tight sandstone gas coalbed methane etc.) coal-based synthetic natural gas imported LNG and imported pipeline gas. The gross calorific value of gas sources ranged from 34 MJ/m3 to 43 MJ/m3 and the maximum difference of calorific value between different gas sources exceeded 20%. On May 24th 2019 the National Development and Reform Commission and other three ministries/commissions jointly issued the Supervision Regulation on the Fair Access of Oil and Gas Pipeline Network Facilities and required that a natural gas energy measuring and pricing system shall be established within 24 months from the implementation date of this Regulation. In order to speed up the construction of China's natural gas energy measuring system this paper summarizes domestic achievements in the construction of natural gas energy measuring system from the aspects of value traceability and energy measurement standard and analyzes natural gas flowrate measurement technology calorific value determination technology value traceability localization intelligentization and application technology of key energy measurement equipment natural gas pipeline network energy balancing technology based on big data analysis multi-source quality tracking and monitoring technology and energy measurement standard system the need of new energy detection and measurement technology and put forward strategy for the development of natural gas measuring in China. And the following research results are obtained. First China's natural gas energy measuring system can basically meet the requirements of implementing natural gas energy measurement but it still falls behind the international leading level in terms of calibration and application of high-level flowmeter (such as 0.5 class) high-accuracy gas reference material level of calorific value reference equipment and measurement standard system and needs to be further improved. Second it is necessary for China to speed up the research and application of the localization and intelligentization technologies of key energy measurement equipment. Third natural gas pipeline network shall be equipped with measurement check method energy balancing system based on big data analysis and multi-source quality tracking and monitoring system so that the energy transmission loss index of natural gas pipeline network can be superior to the international leading level (0.10%). Fourth to realize the large-scale application of hydrogen energy and bio-energy and the mixed transportation of hydrogen bio-methane and natural gas it is necessary to carry out research on new technology and standardization of hydrogen/bio-methane blended natural gas detection and measurement.
A Fracture Analysis of Ti-10Mo-8V-1Fe-3.5Al Alloy Screws during Assembly
Oct 2016
Publication
Titanium screws have properties that make them ideal for applications that require both a high strength-to-weight ratio and corrosion resistance such as fastener applications for aviation and aerospace. The fracture behavior of Ti-10Mo-8V-1Fe-3.5Al (TB3) alloy screws during assembly was explored. Besides visual examination other experimental techniques used for the investigation are as follows: (1) fracture characteristics and damage morphology via scanning electron microscopy (SEM); (2) chemical constituents via energy dispersive spectroscopy (EDS) and hydrogen concentration testing; (3) metallographic observation; (4) stress durability embrittlement testing; and (5) torsion simulation testing. Results show that the fracture mode of the screws is brittle. There is no obvious relation to hydrogen-induced brittle. The main reason for the fracture of titanium alloy screws is internal defects around which oxygen content is high increasing brittleness. The internal defects of screws result from grain boundary cracking caused by hot forging.
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.
Formation Criterion of Hydrogen-Induced Cracking in Steel Based on Fracture Mechanics
Nov 2018
Publication
A new criterion for hydrogen-induced cracking (HIC) that includes both the embrittlement effect and the loading effect of hydrogen was obtained theoretically. The surface cohesive energy and plastic deformation energy are reduced by hydrogen atoms at the interface; thus the fracture toughness is reduced according to fracture mechanics theory. Both the pressure effect and the embrittlement effect mitigate the critical condition required for crack instability extension. During the crack instability expansion the hydrogen in the material can be divided into two categories: hydrogen atoms surrounding the crack and hydrogen molecules in the crack cavity. The loading effect of hydrogen was verified by experiments and the characterization methods for the stress intensity factor under hydrogen pressure in a linear elastic model and an elastoplastic model were analyzed using the finite-element simulation method. The hydrogen pressure due to the aggregation of hydrogen molecules inside the crack cavity regularly contributed to the stress intensity factor. The embrittlement of hydrogen was verified by electrolytic charging hydrogen experiments. According to the change in the atomic distribution during crack propagation in a molecular dynamics simulation the transition from ductile to brittle fracture and the reduction in the fracture toughness were due to the formation of crack tip dislocation regions suppressed by hydrogen. The HIC formation mechanism is both the driving force of crack propagation due to the hydrogen gas pressure and the resisting force reduced by hydrogen atoms.
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.
Recent Advances in Carbon Dioxide Conversion: A Circular Bioeconomy Perspective
Jun 2021
Publication
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.
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.
Life Cycle Assessment of Fuel Cell Vehicles Considering the Detailed Vehicle Components: Comparison and Scenario Analysis in China Based on Different Hydrogen Production Schemes
Aug 2019
Publication
Numerous studies concerning the life cycle assessment of fuel cell vehicles (FCVs) have been conducted. However little attention has been paid to the life cycle assessment of an FCV from the perspective of the detailed vehicle components. This work conducts the life cycle assessment of Toyota Mirai with all major components considered in a Chinese context. Both the vehicle cycle and the fuel cycle are included. Both comprehensive resources and energy consumption and comprehensive environmental emissions of the life cycles are investigated. Potential environmental impacts are further explored based on CML 2001 method. Then different hydrogen production schemes are compared to obtain the most favorable solution. To explore the potential of the electrolysis the scenario analysis of the power structure is conducted. The results show that the most mineral resources are consumed in the raw material acquisition stage the most fossil energy is consumed in the use stage and global warming potential (GWP) value is fairly high in all life cycle stages of Toyota Mirai using electrolyzed hydrogen. For hydrogen production schemes the scenario analysis indicates that simply by optimizing the power structure the environmental impact of the electrolysis remains higher than other schemes. When using the electricity from hydropower or wind power the best choice will be the electrolysis.
Enhanced Hydrogen Storage Properties of Mg by the Synergistic Effect of Grain Refinement and NiTiO 3 Nanoparticles
May 2021
Publication
As a promising hydrogen storage material the practical application of magnesium is obstructed by the stable thermodynamics and sluggish kinetics. In this paper three kinds of NiTiO3 catalysts with different mole ratio of Ni to Ti were successfully synthesized and doped into nanocrystalline Mg to improve its hydrogen storage properties. Experimental results indicated that all the Mg-NiTiO3 composites showed prominent hydrogen storage performance. Especially the Mg-NiTiO3/TiO2 composite could take up hydrogen at room temperature and the apparent activation energy for hydrogen absorption was dramatically decreased from 69.8 ± 1.2 (nanocrystalline Mg) kJ/mol to 34.2 ± 0.2 kJ/mol. In addition the hydrogenated sample began to release hydrogen at about 193.2 °C and eventually desorbed 6.6 wt% H2. The desorption enthalpy of the hydrogenated Mg-NiTiO3 -C was estimated to be 78.6 ± 0.8 kJ/mol 5.3 kJ/mol lower compared to 83.9 ± 0.7 kJ/mol of nanocrystalline Mg. Besides the sample revealed splendid cyclic stability during 20 cycles. No obvious recession occurred in the absorption and desorption kinetics and only 0.3 wt% hydrogen capacity degradation was observed. Further structural analysis demonstrates that nanosizing and catalyst doping led to a synergistic effect on the enhanced hydrogen storage performance of Mg-NiTiO3 -C composite which might serve as a reference for future design of highly effective hydrogen storage materials.
Hydrogen Safety Prediction and Analysis of Hydrogen Refueling Station Leakage Accidents and Process Using Multi-Relevance Machine Learning
Oct 2021
Publication
Hydrogen energy vehicles are being increasingly widely used. To ensure the safety of hydrogenation stations research into the detection of hydrogen leaks is required. Offline analysis using data machine learning is achieved using Spark SQL and Spark MLlib technology. In this study to determine the safety status of a hydrogen refueling station we used multiple algorithm models to perform calculation and analysis: a multi-source data association prediction algorithm a random gradient descent algorithm a deep neural network optimization algorithm and other algorithm models. We successfully analyzed the data including the potential relationships internal relationships and operation laws between the data to detect the safety statuses of hydrogen refueling stations.
Modeling of Fixed Bed Reactor for Coal Tar Hydrogenation via the Kinetic Lumping Approach
Nov 2018
Publication
Hydrogenation technology is an indispensable chemical upgrading process for converting the heavy feedstock into favorable lighter products. In this work a new kinetic model containing four hydrocarbon lumps (feedstock diesel gasoline cracking gas) was developed to describe the coal tar hydrogenation process the Levenberg–Marquardt’s optimization algorithm was used to determine the kinetic parameters by minimizing the sum of square errors between experimental and calculated data the predictions from model validation showed a good agreement with experimental values. Subsequently an adiabatic reactor model based on proposed lumped kinetic model was constructed to further investigate the performance of hydrogenation fixed-bed units the mass balance and energy balance within the phases in the reactor were taken into accounts in the form of ordinary differential equation. An application of the reactor model was performed for simulating the actual bench-scale plant of coal tar hydrogenation the simulated results on the products yields and temperatures distribution along with the reactor are shown to be good consistent with the experimental data.
Influence of Synthesis Gas Components on Hydrogen Storage Properties of Sodium Aluminium Hexahydride
Feb 2021
Publication
A systematic study of different ratios of CO CO2 N2 gas components on the hydrogen storage properties of the Na3AlH6 complex hydride with 4 mol% TiCl3 8 mol% aluminum and 8 mol% activated carbon is presented in this paper. The different concentrations of CO and CO2in H2 and CO CO2 N2 in H2 mixture were investigated. Both CO and CO2gas react with the complex hydride forming Al oxy-compounds NaOH and Na2CO3 that consequently cause serious decline in hydrogen storage capacity. These reactions lead to irreversible damage of complex hydride under the current experimental condition. Thus after 10 cycles with 0.1 vol % CO + 99.9 vol %H2 and 1 vol % CO + 99 vol %H2 the dehydrogenation storage capacity of the composite material decreased by 17.2% and 57.3% respectively. In the case of investigation of 10 cycles with 1 vol % CO2 + 99 vol % H2 gas mixture the capacity degradation was 53.5%. After 2 cycles with 10 vol % CO +90 vol % H2 full degradation was observed whereas after 6 cycles with 10 vol % CO2+ 90 vol % H2 degradation of 86.8% was measured. While testing with the gas mixture of 1.5 vol % CO + 10 vol % CO2+ 27 vol % H2 + 61.5 vol % N2 the degradation of 94% after 6 cycles was shown. According to these results it must be concluded that complex aluminum hydrides cannot be used for the absorption of hydrogen from syngas mixtures without thorough purification.
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