The almost completely dense copper was prepared by ultrafine copper powder prepared with both methods of electrolysis and novel water-gas atomization through cold isostatic pressing(CIP)and sintering under atmospheric...The almost completely dense copper was prepared by ultrafine copper powder prepared with both methods of electrolysis and novel water-gas atomization through cold isostatic pressing(CIP)and sintering under atmospheric hydrogen.Fine copper powder possesses the higher sintering driving force,thereby promoting shrinkage and densification during the sintering process.The grain size of sintered samples by electrolytic copper powder is smaller than that prepared by the atomized copper powder,and the twin crystals are particularly prone to forming in the former sintered microstructure due to the raw powder with low oxygen content and high residual stress originating from the CIP process.The relative density of samples by electrolytic and atomized powder at 1000℃ sintering temperature achieves 99.3%and 97.4%,respectively,significantly higher than that of the powder metallurgy copper parts reported in the literature.Correspondingly,the ultimate tensile strength and yield strength of samples by both kinds of copper powder are approximately similar,while the elongation of the sintered sample by the electrolytic powder(60%)is apparently higher than the atomized powder(44%).The superior performance of samples fabricated by electrolytic powder is inferred from the full density and low oxygen level for there is no cuprous oxide in the grain boundaries.展开更多
Attaining a decarbonized and sustainable energy system,which is the core solution to global energy issues,is accessible through the development of hydrogen energy.Proton-exchange membrane water electrolyzers(PEMWEs)ar...Attaining a decarbonized and sustainable energy system,which is the core solution to global energy issues,is accessible through the development of hydrogen energy.Proton-exchange membrane water electrolyzers(PEMWEs)are promising devices for hydrogen production,given their high efficiency,rapid responsiveness,and compactness.Bipolar plates account for a relatively high percentage of the total cost and weight compared with other components of PEMWEs.Thus,optimization of their design may accelerate the promotion of PEMWEs.This paper reviews the advances in materials and flow-field design for bipolar plates.First,the working conditions of proton-exchange membrane fuel cells(PEMFCs)and PEMWEs are compared,including reaction direction,operating temperature,pressure,input/output,and potential.Then,the current research status of bipolar-plate substrates and surface coatings is summarized,and some typical channel-rib flow fields and porous flow fields are presented.Furthermore,the effects of materials on mass and heat transfer and the possibility of reducing corrosion by improving the flow field structure are explored.Finally,this review discusses the potential directions of the development of bipolar-plate design,including material fabrication,flow-field geometry optimization using threedimensional printing,and surface-coating composition optimization based on computational materials science.展开更多
While carbon dioxide(CO_(2))is a major greenhouse gas,it is also an important C1 resource.In the trend of energy conservation and emission reduction,electrocatalytic reduction has become a very promising strategy for ...While carbon dioxide(CO_(2))is a major greenhouse gas,it is also an important C1 resource.In the trend of energy conservation and emission reduction,electrocatalytic reduction has become a very promising strategy for CO_(2)utilization because it can convert CO_(2)directly to high-valued chemicals and fuels under mild conditions.In particular,the product CO and by-product H_(2)can be combined into syngas by an electrocatalytic CO_(2)reduction reaction(CO_(2)RR)in an aqueous medium.Different molar ratios of CO and H_(2)may be used to produce essential bulk chemicals or liquid fuels such as methanol,alkanes,and olefins through thermochemical catalysis,Fischer-Tropsch synthesis,microbial fermentation,and other techniques.This work discusses the latest strategies in controlling the molar ratio of CO/H_(2)and improving the yield of CO_(2)RR-to-syngas.The challenges of electrocatalytic syngas production are analyzed from an industrial application perspective,and the possible measures to overcome them are proposed in terms of new catalyst design,electrolyte innovation,flow reactor optimization,anodic reaction coupling,and operando technique application.展开更多
Herein,we have designed a highly active and robust trifunctional electrocatalyst derived from Prussian blue analogs,where Co_(4)N nanoparticles are encapsulated by Fe embedded in N-doped carbon nanocubes to synthesize...Herein,we have designed a highly active and robust trifunctional electrocatalyst derived from Prussian blue analogs,where Co_(4)N nanoparticles are encapsulated by Fe embedded in N-doped carbon nanocubes to synthesize hierarchically structured Co_(4)N@Fe/N-C for rechargeable zinc-air batteries and overall water-splitting electrolyzers.As confirmed by theoretical and experimental results,the high intrinsic oxygen reduction reaction,oxygen evolution reaction,and hydrogen evolution reaction activities of Co_(4)N@Fe/N-C were attributed to the formation of the heterointerface and the modulated local electronic structure.Moreover,Co_(4)N@Fe/N-C induced improvement in these trifunctional electrocatalytic activities owing to the hierarchical hollow nanocube structure,uniform distribution of Co_(4)N,and conductive encapsulation by Fe/N-C.Thus,the rechargeable zinc-air battery with Co_(4)N@Fe/N-C delivers a high specific capacity of 789.9 mAh g^(-1) and stable voltage profiles over 500 cycles.Furthermore,the overall water electrolyzer with Co_(4)N@Fe/N-C achieved better durability and rate performance than that with the Pt/C and IrO2 catalysts,delivering a high Faradaic efficiency of 96.4%.Along with the great potential of the integrated water electrolyzer powered by a zinc-air battery for practical applications,therefore,the mechanistic understanding and active site identification provide valuable insights into the rational design of advanced multifunctional electrocatalysts for energy storage and conversion.展开更多
Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single prod...Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single product.Herein,we report a simple fabrication method for a Cu-Pd alloy catalyst for use in a membrane electrode assembly(MEA)-based CO_(2) electrolyzer for the electrochemical CO_(2) reduction reaction(ECRR)with high selectivity for CO production.When the composition of the Cu-Pd alloy catalyst was fabricated at 6:4,the selectivity for CO increased and the production of multi-carbon compounds and hydrogen is suppressed.Introducing a Cu-Pd alloy catalyst with 6:4 ratio as the cathode of the MEAbased CO_(2) electrolyzer showed a CO faradaic efficiency of 92.8%at 2.4 V_(cell).We assumed that these results contributed from the crystal planes on the surface of the Cu-Pd alloy.The phases of the Cu-Pd alloy catalyst were partially separated through annealing to fabricate a catalyst with high selectivity for CO at low voltage and C_(2)H_4 at high voltage.The results of CO-stripping testing confirmed that when Cu partially separates from the lattice of the Cu-Pd alloy,the desorption of~*CO is suppressed,suggesting that C-C coupling reaction is favored.展开更多
Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal int...Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.展开更多
Glucosinolates are important phytochemicals in Brassicaceae.We investigated the effect of CaCl_(2)-HCl electrolyzed water(CHEW)on glucosinolates biosynthesis in broccoli sprouts.The results showed that CHEW treatment ...Glucosinolates are important phytochemicals in Brassicaceae.We investigated the effect of CaCl_(2)-HCl electrolyzed water(CHEW)on glucosinolates biosynthesis in broccoli sprouts.The results showed that CHEW treatment significantly decreased reactive oxygen species(ROS)and malondialdeh yde(MDA)contents in broccoli sprouts.On the the 8^(th)day,compared to tap water treatment,the the total glucosinolate content of broccoli sprouts with CHEW treatment increased by 10.6%and calcium content was dramatically enhanced from 14.4 mg/g DW to 22.7 mg/g DW.Comparative transcriptome and metabolome analyses revealed that CHEW treatment activated ROS and calcium signaling transduction pathways in broccoli sprouts and they interacted through MAPK cascades.Besides,CHEW treatment not only promoted the biosynthesis of amino acids,but also enhanced the expression of structural genes in glucosinolate synthesis through transcription factors(MYBs,bHLHs,WRKYs,etc.).The results of this study provided new insights into the regulatory network of glucosinolates biosynthesis in broccoli sprouts under CHEW treatment.展开更多
The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen pro...The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen production technologies,anion exchange membrane water electrolyzer(AEMWE)has emerged as a next-generation technology known for its high hydrogen production efficiency and its ability to use non-metal catalysts.However,this technology faces significant challenges,particularly in terms of the membrane durability and low ionic conductivity.To address these challenges,research efforts have focused on developing membranes with a new backbone structure and anion exchange groups to enhance durability and ionic conductivity.Notably,the super-acid-catalyzed condensation(SACC)synthesis method stands out due to its user convenience,the ability to create high molecular weight(MW)polymers,and the use of oxygen-tolerant organic catalysts.Although the synthesis of anion exchange membranes(AEMs)using the SACC method began in 2015,and despite growing interest in this synthesis approach,there remains a scarcity of review papers focusing on AEMs synthesized using the SACC method.The review covers the basics of SACC synthesis,presents various polymers synthesized using this method,and summarizes the development of these polymers,particularly their building blocks including aryl,ketone,and anion exchange groups.We systematically describe the effects of changes in the molecular structure of each polymer component,conducted by various research groups,on the mechanical properties,conductivity,and operational stability of the membrane.This review will provide insights into the development of AEMs with superior performance and operational stability suitable for water electrolysis applications.展开更多
We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed ...We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.展开更多
Hydrogen production by proton exchange membrane electrolysis has good fluctuation adaptability,making it suitable for hydrogen production by electrolysis in fluctuating power sources such as wind power.However,current...Hydrogen production by proton exchange membrane electrolysis has good fluctuation adaptability,making it suitable for hydrogen production by electrolysis in fluctuating power sources such as wind power.However,current research on the durability of proton exchange membrane electrolyzers is insufficient.Studying the typical operating conditions of wind power electrolysis for hydrogen production can provide boundary conditions for performance and degradation tests of electrolysis stacks.In this study,the operating condition spectrum of an electrolysis stack degradation test cycle was proposed.Based on the rate of change of the wind farm output power and the time-averaged peak-valley difference,a fluctuation output power sample set was formed.The characteristic quantities that played an important role in the degradation of the electrolysis stack were selected.Dimensionality reduction of the operating data was performed using principal component analysis.Clustering analysis of the data segments was completed using an improved Gaussian mixture clustering algorithm.Taking the annual output power data of wind farms in Northwest China with a sampling rate of 1 min as an example,the cyclic operating condition spectrum of the proton-exchange membrane electrolysis stack degradation test was constructed.After preliminary simulation analysis,the typical operating condition proposed in this paper effectively reflects the impact of the original curve on the performance degradation of the electrolysis stack.This study provides a method for evaluating the degradation characteristics and system efficiency of an electrolysis stack due to fluctuations in renewable energy.展开更多
Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm...Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm,electrodes,bipolar plates and end plates,etc.The existing industrial bipolar plate channel is concave-convex structure,which is manufactured by complicated and high-cost mold punching.This structure still results in uneven electrolyte flow and low current density in the electrolytic cell,further increasing in energy consumption and cost of AWE.Thereby,in this article,the electrochemical and flow model is firstly constructed,based on the existing industrial concave and convex flow channel structure of bipolar plate,to study the current density,electrolyte flow and bubble distribution in the electrolysis cell.The reliability of the model was verified by comparison with experimental data in literature.Among which,the electrochemical current density affects the bubble yield,on the other hand,the generated bubbles cover the electrode surface,affecting the active specific surface area and ohmic resistance,which in turn affects the electrochemical reaction.The result indicates that the flow velocity near the bottom of the concave ball approaches zero,while the flow velocity on the convex ball surface is significantly higher.Additionally,vortices are observed within the flow channel structure,leading to an uneven distribution of electrolyte.Next,modelling is used to optimize the bipolar plate structure of AWE by simulating the electrochemistry and fluid flow performances of four kinds of structures,namely,concave and convex,rhombus,wedge and expanded mesh,in the bipolar plate of alkaline water electrolyzer.The results show that the expanded mesh channel structure has the largest current density of 3330 A/m^(2)and electrolyte flow velocity of 0.507 m/s in the electrolytic cell.Under the same current density,the electrolytic cell with the expanded mesh runner structure has the smallest potential and energy consumption.This work provides a useful guide for the comprehensive understanding and optimization of channel structures,and a theoretical basis for the design of large-scale electrolyzer.展开更多
In the existing power system with a large-scale hydrogen storage system,there are problems such as low efficiency of electric-hydrogen-electricity conversion and single modeling of the hydrogen storage system.In order...In the existing power system with a large-scale hydrogen storage system,there are problems such as low efficiency of electric-hydrogen-electricity conversion and single modeling of the hydrogen storage system.In order to improve the hydrogen utilization rate of hydrogen storage system in the process of participating in the power grid operation,and speed up the process of electric-hydrogen-electricity conversion.This article provides a detailed introduction to the mathematical and electrical models of various components of the hydrogen storage unit,and also establishes a charging and discharging efficiency model that considers the temperature and internal gas partial pressure of the hydrogen storage unit.These models are of great significance for studying and optimizing gas storage technology.Through these models,the performance of gas storage units can be better understood and improved.These studies are very helpful for improving energy storage efficiency and sustainable development.The factors affecting the charge-discharge efficiency of hydrogen storage units are analyzed.By integrating the models of each unit and considering the capacity degradation of the hydrogen storage system,we can construct an efficiency model for a large hydrogen storage system and power conversion system.In addition,the simulation models of the hydrogen production system and hydrogen consumption system were established in MATLAB/Simulink.The accuracy and effectiveness of the simulation model were proved by comparing the output voltage variation curve of the simulation with the polarization curve of the typical hydrogen production system and hydrogen consumption system.The results show that the charge-discharge efficiency of the hydrogen storage unit increases with the increase of operating temperature,and H2 and O2 partial voltage have little influence on the charge-discharge efficiency.In the process of power conversion system converter rectification operation,its efficiency decreases with the increase of temperature,while in the process of inverter operation,power conversion system efficiency increases with the increase of temperature.Combined with the efficiency of each hydrogen storage unit and power conversion system converter,the upper limit of the capacity loss of different hydrogen storage units was set.The optimal charge-discharge efficiency of the hydrogen storage system was obtained by using the Cplex solver at 36.46%and 66.34%.展开更多
The rise in hydrogen production powered by renewable energy is driving the field toward the adoption of systems comprising multiple alkaline water electrolyzers.These setups present various operational modes:independe...The rise in hydrogen production powered by renewable energy is driving the field toward the adoption of systems comprising multiple alkaline water electrolyzers.These setups present various operational modes:independent operation and multi-electrolyzer parallelization,each with distinct advantages and challenges.This study introduces an innovative configuration that incorporates a mutual lye mixer among electrolyzers,establishing a weakly coupled system that combines the advantages of two modes.This approach enables efficient heat utilization for faster hot-startup and maintains heat conservation post-lye interconnection,while preserving the option for independent operation after decoupling.A specialized thermal exchange model is developed for this topology,according to the dynamics of the lye mixer.The study further details startup procedures and proposes optimized control strategies tailored to this structural design.Waste heat from the caustic fully heats up the multiple electrolyzers connected to the lye mixing system,enabling a rapid hot start to enhance the system’s ability to track renewable energy.A control strategy is established to reduce heat loss and increase startup speed,and the optimal valve openings of the diverter valve and the manifold valve are determined.Simulation results indicate a considerable enhancement in operational efficiency,marked by an 18.28%improvement in startup speed and a 6.11%reduction in startup energy consumption inmulti-electrolyzer cluster systems,particularlywhen the systems are synchronized with photovoltaic energy sources.The findings represent a significant stride toward efficient and sustainable hydrogen production,offering a promising path for large-scale integration of renewable energy.展开更多
Hydrogen has been regarded as a promising renewable and green energy source to meet energy needs and attain net-zero carbon emissions.The electrolysis of seawater to make hydrogen is one of the fascinating development...Hydrogen has been regarded as a promising renewable and green energy source to meet energy needs and attain net-zero carbon emissions.The electrolysis of seawater to make hydrogen is one of the fascinating developments of the twenty-first century.This method uses abundant and relatively inexpensive seawater,as opposed to freshwater,which is rare and can be prohibitively expensive.In recent years,significant research and advancements have been made in direct seawater electrolysis technology for hydrogen production.However,producing highly effective and efficient electrocatalysts with long-term viability under harsh corrosive conditions remains a challenging and severe topic for large-scale seawater electrolysis technology.There is still a large accomplishment gap in understanding how to improve seawater electrolysis to increase hydrogen yields and prolong stability.It is,therefore,crucial to have a condensed knowledge of the tunable and inherent interactions between various electrocatalysts,covering electrolyzer types and paying particular attention to those with high efficiency,chemical stability,and conductivity.The extensive discussion is structured into a progression from noble metals to base metal compounds such as oxides,alloys,phosphides,chalcogenides,hydroxides,and nitrides,MXene-based complexes with a concise examination of hybrid electrocatalysts.In addition,proton exchange membranes,anion exchange membranes,alkaline water electrolyzers,and high-temperature water electrolyzers were potential contributors to seawater’s electrolysis.An extensive assessment of the techno-feasibility,economic insights,and future suggestions was done to commercialize the most efficient electrocatalytic systems for hydrogen production.This review is anticipated to provide academics,environmentalists,and industrial researchers with valuable ideas for constructing and modifying seawater-based electrocatalysts.展开更多
Electrocatalytic splitting of water by means of renewable energy as the electricity supply is one of the most promising methods for storing green renewable energy as hydrogen. Although two-thirds of the earth’s surfa...Electrocatalytic splitting of water by means of renewable energy as the electricity supply is one of the most promising methods for storing green renewable energy as hydrogen. Although two-thirds of the earth’s surface is covered with water, there is inadequacy of freshwater in most parts of the world. Hence, splitting seawater instead of freshwater could be a truly sustainable alternative. However, direct seawater splitting faces challenges because of the complex composition of seawater. The composition, and hence, the local chemistry of seawater may vary depending on its origin, and in most cases, tracking of the side reactions and standardizing and customizing the catalytic process will be an extra challenge. The corrosion of catalysts and competitive side reactions due to the presence of various inorganic and organic pollutants create challenges for developing stable electro-catalysts. Hence, seawater splitting generally involves a two-step process, i.e., purification of seawater using reverse osmosis and then subsequent fresh water splitting. However, this demands two separate chambers and larger space, and increases complexity of the reactor design. Recently, there have been efforts to directly split seawater without the reverse osmosis step. Herein, we represent the most recent innovative approaches to avoid the two-step process, and compare the potential application of membrane-assisted and membrane-less electrolyzers in direct seawater splitting(DSS). We particularly discuss the device engineering, and propose a novel electrolyzer design strategies for concentration gradient based membrane-less microfluidic electrolyzer.展开更多
Anion exchange membrane(AEM)electrolysis is a promising membrane-based green hydrogen production technology.However,AEM electrolysis still remains in its infancy,and the performance of AEM electrolyzers is far behind ...Anion exchange membrane(AEM)electrolysis is a promising membrane-based green hydrogen production technology.However,AEM electrolysis still remains in its infancy,and the performance of AEM electrolyzers is far behind that of well-developed alkaline and proton exchange membrane electrolyzers.Therefore,breaking through the technical barriers of AEM electrolyzers is critical.On the basis of the analysis of the electrochemical performance tested in a single cell,electrochemical impedance spectroscopy,and the number of active sites,we evaluated the main technical factors that affect AEM electrolyzers.These factors included catalyst layer manufacturing(e.g.,catalyst,carbon black,and anionic ionomer)loadings,membrane electrode assembly,and testing conditions(e.g.,the KOH concentration in the electrolyte,electrolyte feeding mode,and operating temperature).The underlying mechanisms of the effects of these factors on AEM electrolyzer performance were also revealed.The irreversible voltage loss in the AEM electrolyzer was concluded to be mainly associated with the kinetics of the electrode reaction and the transport of electrons,ions,and gas-phase products involved in electrolysis.Based on the study results,the performance and stability of AEM electrolyzers were significantly improved.展开更多
To analyze the additional cost caused by the performance attenuation of a proton exchange membrane electrolyzer(PEMEL)under the fluctuating input of renewable energy,this study proposes an optimization method for powe...To analyze the additional cost caused by the performance attenuation of a proton exchange membrane electrolyzer(PEMEL)under the fluctuating input of renewable energy,this study proposes an optimization method for power scheduling in hydrogen production systems under the scenario of photovoltaic(PV)electrolysis of water.First,voltage and performance attenuation models of the PEMEL are proposed,and the degradation cost of the electrolyzer under a fluctuating input is considered.Then,the calculation of the investment and operating costs of the hydrogen production system for a typical day is based on the life cycle cost.Finally,a layered power scheduling optimization method is proposed to reasonably distribute the power of the electrolyzer and energy storage system in a hydrogen production system.In the up-layer optimization,the PV power absorbed by the hydrogen production system was optimized using MALTAB+Gurobi.In low-layer optimization,the power allocation between the PEMEL and battery energy storage system(BESS)is optimized using a non-dominated sorting genetic algorithm(NSGA-Ⅱ)combined with the firefly algorithm(FA).A better optimization result,characterized by lower degradation and total costs,was obtained using the method proposed in this study.The improved algorithm can search for a better population and obtain optimization results in fewer iterations.As a calculation example,data from a PV power station in northwest China were used for optimization,and the effectiveness and rationality of the proposed optimization method were verified.展开更多
Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realiz...Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realize the storage of renewable energy,for it guarantees the production of value-added chemicals and fuels.Among CO_(2)RR products,formic acid shows great advantages in low energy consumption and high added-value,and thus producing formic acid is generally considered as a profitable line for CO_(2)RR.Bismuth-based electrocatalysts exhibit high formic acid selectivity in CO_(2)RR.Herein,we review the recent progress in bismuth-based electrocatalysts for CO_(2)RR,including material synthesis,performance optimization/validation,and electrolyzers.The effects of morphologies,structure,and composition of bismuth-based electrocatalysts on CO_(2)RR performance are highlighted.Simultaneously,in situ spectroscopic characterization and DFT calculations for reaction mechanism of CO_(2)RR on Bi-based catalysts are emphasized.The applications and optimization of electrolyzers with high current density for CO_(2)RR are summarized.Finally,conclusions and future directions in this field are prospected.展开更多
CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at desi...CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at design and understanding of catalytic materials and electrolyte systems,the CO_(2) ER performance(such as current density,selectivity,stability,CO_(2) conversion,etc.)has been continually increased.Unfortunately,there has been relatively little attention paid to the large-scale CO 2 electrolyzers,which stand just as one obstacle,alongside series-parallel integration,challenging the practical application of this infant technology.In this review,the latest progress on the structures of low-temperature CO_(2) electrolyzers and scale-up studies was systematically overviewed.The influence of the CO_(2) electrolyzer configurations,such as the flow channel design,gas diffusion electrode(GDE)and ion exchange membrane(IEM),on the CO_(2) ER performance was further discussed.The review could provide inspiration for the design of large-scale CO_(2) electrolyzers so as to accelerate the industrial application of CO_(2) ER technology.展开更多
Prussian blue analogues(PBAs) with inherent ordered structures and abundant metal ion sites are widely explored as precursors for various electrochemical applications,including oxygen evolution reaction(OER).Using a r...Prussian blue analogues(PBAs) with inherent ordered structures and abundant metal ion sites are widely explored as precursors for various electrochemical applications,including oxygen evolution reaction(OER).Using a range of characterization techniques including Fourier-transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and energy dispersive spectroscopy(EDS),this work discloses the process of replacement of K^(+)by NH4^(+)in the interstitial spaces of the CoFe PBA by a hot aqueous urea solution,which influences the transformation of PBAs under further heat treatment and the OER performance of the deriva tives.After heat treatment at 400℃ under Ar flow,high-resolution transmission electron microscopy(HRTEM) images reveal that CoFe alloy nanoparticles grew on the crystalline cubes of CoFe PBA with K^(+),while CoFe PBA cubes with NH4^(+)become amorphous.Besides,the derivative of CoFe PBA with NH4^(+)(Ar-U-CoFe PBA) performs better than the derivative of CoFe PBA with K^(+)(Ar-CoFe PBA) in OER,registering a lower overpotential of 305 mV at 10 mA cm^(-2),a smaller Tafel slope of 36.1 mV dec^(-1),and better stability over a testing course of 20 h in 1.0 M KOH.A single-cell alkaline electrolyzer,using Ar-U-CoFe PBA and Pt/C for the anodic and cathodic catalyst,respectively,requires an initial cell voltage of 1.66 V to achieve 100 mA cm^(-2)at 80℃,with negligible degradation after100 h.展开更多
基金Project(92066205)supported by the National Natural Science Foundation of ChinaProject(2019-Z10)supported by the State Key Lab for Advanced Metals and Materials of ChinaProject(FRF-MP-20-52)supported by the Fundamental Research Funds for the Central Universities,China。
文摘The almost completely dense copper was prepared by ultrafine copper powder prepared with both methods of electrolysis and novel water-gas atomization through cold isostatic pressing(CIP)and sintering under atmospheric hydrogen.Fine copper powder possesses the higher sintering driving force,thereby promoting shrinkage and densification during the sintering process.The grain size of sintered samples by electrolytic copper powder is smaller than that prepared by the atomized copper powder,and the twin crystals are particularly prone to forming in the former sintered microstructure due to the raw powder with low oxygen content and high residual stress originating from the CIP process.The relative density of samples by electrolytic and atomized powder at 1000℃ sintering temperature achieves 99.3%and 97.4%,respectively,significantly higher than that of the powder metallurgy copper parts reported in the literature.Correspondingly,the ultimate tensile strength and yield strength of samples by both kinds of copper powder are approximately similar,while the elongation of the sintered sample by the electrolytic powder(60%)is apparently higher than the atomized powder(44%).The superior performance of samples fabricated by electrolytic powder is inferred from the full density and low oxygen level for there is no cuprous oxide in the grain boundaries.
基金the National Natural Science Foundation of China(No.52125102)the National Key Research and Development Program of China(No.2021YFB4000101)Fundamental Research Funds for t he Central Universities(No.FRF-TP-2021-02C2)。
文摘Attaining a decarbonized and sustainable energy system,which is the core solution to global energy issues,is accessible through the development of hydrogen energy.Proton-exchange membrane water electrolyzers(PEMWEs)are promising devices for hydrogen production,given their high efficiency,rapid responsiveness,and compactness.Bipolar plates account for a relatively high percentage of the total cost and weight compared with other components of PEMWEs.Thus,optimization of their design may accelerate the promotion of PEMWEs.This paper reviews the advances in materials and flow-field design for bipolar plates.First,the working conditions of proton-exchange membrane fuel cells(PEMFCs)and PEMWEs are compared,including reaction direction,operating temperature,pressure,input/output,and potential.Then,the current research status of bipolar-plate substrates and surface coatings is summarized,and some typical channel-rib flow fields and porous flow fields are presented.Furthermore,the effects of materials on mass and heat transfer and the possibility of reducing corrosion by improving the flow field structure are explored.Finally,this review discusses the potential directions of the development of bipolar-plate design,including material fabrication,flow-field geometry optimization using threedimensional printing,and surface-coating composition optimization based on computational materials science.
基金the financial support from the National Natural Science Foundation of China(22233006,22273018)the Project of Henan International Joint Laboratory of Green Chemistrythe 111 Project(D17007)。
文摘While carbon dioxide(CO_(2))is a major greenhouse gas,it is also an important C1 resource.In the trend of energy conservation and emission reduction,electrocatalytic reduction has become a very promising strategy for CO_(2)utilization because it can convert CO_(2)directly to high-valued chemicals and fuels under mild conditions.In particular,the product CO and by-product H_(2)can be combined into syngas by an electrocatalytic CO_(2)reduction reaction(CO_(2)RR)in an aqueous medium.Different molar ratios of CO and H_(2)may be used to produce essential bulk chemicals or liquid fuels such as methanol,alkanes,and olefins through thermochemical catalysis,Fischer-Tropsch synthesis,microbial fermentation,and other techniques.This work discusses the latest strategies in controlling the molar ratio of CO/H_(2)and improving the yield of CO_(2)RR-to-syngas.The challenges of electrocatalytic syngas production are analyzed from an industrial application perspective,and the possible measures to overcome them are proposed in terms of new catalyst design,electrolyte innovation,flow reactor optimization,anodic reaction coupling,and operando technique application.
基金National Research Foundation of Korea,Grant/Award Numbers:NRF-2020R1A3B2079803,2021R1A2C2007804。
文摘Herein,we have designed a highly active and robust trifunctional electrocatalyst derived from Prussian blue analogs,where Co_(4)N nanoparticles are encapsulated by Fe embedded in N-doped carbon nanocubes to synthesize hierarchically structured Co_(4)N@Fe/N-C for rechargeable zinc-air batteries and overall water-splitting electrolyzers.As confirmed by theoretical and experimental results,the high intrinsic oxygen reduction reaction,oxygen evolution reaction,and hydrogen evolution reaction activities of Co_(4)N@Fe/N-C were attributed to the formation of the heterointerface and the modulated local electronic structure.Moreover,Co_(4)N@Fe/N-C induced improvement in these trifunctional electrocatalytic activities owing to the hierarchical hollow nanocube structure,uniform distribution of Co_(4)N,and conductive encapsulation by Fe/N-C.Thus,the rechargeable zinc-air battery with Co_(4)N@Fe/N-C delivers a high specific capacity of 789.9 mAh g^(-1) and stable voltage profiles over 500 cycles.Furthermore,the overall water electrolyzer with Co_(4)N@Fe/N-C achieved better durability and rate performance than that with the Pt/C and IrO2 catalysts,delivering a high Faradaic efficiency of 96.4%.Along with the great potential of the integrated water electrolyzer powered by a zinc-air battery for practical applications,therefore,the mechanistic understanding and active site identification provide valuable insights into the rational design of advanced multifunctional electrocatalysts for energy storage and conversion.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government MSIT(2021R1A2C2093358,2021R1A4A3027878,2022M3I3A1081901)financial support from the Lotte Chemical Company。
文摘Cu catalysts can convert CO_(2) through an electrochemical reduction reaction into a variety of useful carbon-based products.However,this capability provides an obstacle to increasing the selectivity for a single product.Herein,we report a simple fabrication method for a Cu-Pd alloy catalyst for use in a membrane electrode assembly(MEA)-based CO_(2) electrolyzer for the electrochemical CO_(2) reduction reaction(ECRR)with high selectivity for CO production.When the composition of the Cu-Pd alloy catalyst was fabricated at 6:4,the selectivity for CO increased and the production of multi-carbon compounds and hydrogen is suppressed.Introducing a Cu-Pd alloy catalyst with 6:4 ratio as the cathode of the MEAbased CO_(2) electrolyzer showed a CO faradaic efficiency of 92.8%at 2.4 V_(cell).We assumed that these results contributed from the crystal planes on the surface of the Cu-Pd alloy.The phases of the Cu-Pd alloy catalyst were partially separated through annealing to fabricate a catalyst with high selectivity for CO at low voltage and C_(2)H_4 at high voltage.The results of CO-stripping testing confirmed that when Cu partially separates from the lattice of the Cu-Pd alloy,the desorption of~*CO is suppressed,suggesting that C-C coupling reaction is favored.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.
基金supported by the National Natural Science Foundation of China(31972091)。
文摘Glucosinolates are important phytochemicals in Brassicaceae.We investigated the effect of CaCl_(2)-HCl electrolyzed water(CHEW)on glucosinolates biosynthesis in broccoli sprouts.The results showed that CHEW treatment significantly decreased reactive oxygen species(ROS)and malondialdeh yde(MDA)contents in broccoli sprouts.On the the 8^(th)day,compared to tap water treatment,the the total glucosinolate content of broccoli sprouts with CHEW treatment increased by 10.6%and calcium content was dramatically enhanced from 14.4 mg/g DW to 22.7 mg/g DW.Comparative transcriptome and metabolome analyses revealed that CHEW treatment activated ROS and calcium signaling transduction pathways in broccoli sprouts and they interacted through MAPK cascades.Besides,CHEW treatment not only promoted the biosynthesis of amino acids,but also enhanced the expression of structural genes in glucosinolate synthesis through transcription factors(MYBs,bHLHs,WRKYs,etc.).The results of this study provided new insights into the regulatory network of glucosinolates biosynthesis in broccoli sprouts under CHEW treatment.
基金supported by the KRISS(Korea Research Institute of Standards and Science)MPI Lab.program。
文摘The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen production technologies,anion exchange membrane water electrolyzer(AEMWE)has emerged as a next-generation technology known for its high hydrogen production efficiency and its ability to use non-metal catalysts.However,this technology faces significant challenges,particularly in terms of the membrane durability and low ionic conductivity.To address these challenges,research efforts have focused on developing membranes with a new backbone structure and anion exchange groups to enhance durability and ionic conductivity.Notably,the super-acid-catalyzed condensation(SACC)synthesis method stands out due to its user convenience,the ability to create high molecular weight(MW)polymers,and the use of oxygen-tolerant organic catalysts.Although the synthesis of anion exchange membranes(AEMs)using the SACC method began in 2015,and despite growing interest in this synthesis approach,there remains a scarcity of review papers focusing on AEMs synthesized using the SACC method.The review covers the basics of SACC synthesis,presents various polymers synthesized using this method,and summarizes the development of these polymers,particularly their building blocks including aryl,ketone,and anion exchange groups.We systematically describe the effects of changes in the molecular structure of each polymer component,conducted by various research groups,on the mechanical properties,conductivity,and operational stability of the membrane.This review will provide insights into the development of AEMs with superior performance and operational stability suitable for water electrolysis applications.
基金National Research Foundation of Korea,Grant/Award Numbers:2019H1D3A1A01071209,2021R1I1A1A01060380,2022R1A2C2010686,2022R1A4A3033528Korea Basic Science Institute,Grant/Award Numbers:2019R1A6C1010042,2021R1A6C103A427。
文摘We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.
基金supported by the National Key Research and Development Program of China(Materials and Process Basis of Electrolytic Hydrogen Production from Fluctuating Power Sources such as Photovoltaic/Wind Power,No.2021YFB4000100).
文摘Hydrogen production by proton exchange membrane electrolysis has good fluctuation adaptability,making it suitable for hydrogen production by electrolysis in fluctuating power sources such as wind power.However,current research on the durability of proton exchange membrane electrolyzers is insufficient.Studying the typical operating conditions of wind power electrolysis for hydrogen production can provide boundary conditions for performance and degradation tests of electrolysis stacks.In this study,the operating condition spectrum of an electrolysis stack degradation test cycle was proposed.Based on the rate of change of the wind farm output power and the time-averaged peak-valley difference,a fluctuation output power sample set was formed.The characteristic quantities that played an important role in the degradation of the electrolysis stack were selected.Dimensionality reduction of the operating data was performed using principal component analysis.Clustering analysis of the data segments was completed using an improved Gaussian mixture clustering algorithm.Taking the annual output power data of wind farms in Northwest China with a sampling rate of 1 min as an example,the cyclic operating condition spectrum of the proton-exchange membrane electrolysis stack degradation test was constructed.After preliminary simulation analysis,the typical operating condition proposed in this paper effectively reflects the impact of the original curve on the performance degradation of the electrolysis stack.This study provides a method for evaluating the degradation characteristics and system efficiency of an electrolysis stack due to fluctuations in renewable energy.
基金financially supported by the National Natural Science Foundation of China(No.52074130)the Engineering Research Center of Resource Utilization of Carbon-containing Waste with Carbon Neutrality,Ministry of Education。
文摘Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm,electrodes,bipolar plates and end plates,etc.The existing industrial bipolar plate channel is concave-convex structure,which is manufactured by complicated and high-cost mold punching.This structure still results in uneven electrolyte flow and low current density in the electrolytic cell,further increasing in energy consumption and cost of AWE.Thereby,in this article,the electrochemical and flow model is firstly constructed,based on the existing industrial concave and convex flow channel structure of bipolar plate,to study the current density,electrolyte flow and bubble distribution in the electrolysis cell.The reliability of the model was verified by comparison with experimental data in literature.Among which,the electrochemical current density affects the bubble yield,on the other hand,the generated bubbles cover the electrode surface,affecting the active specific surface area and ohmic resistance,which in turn affects the electrochemical reaction.The result indicates that the flow velocity near the bottom of the concave ball approaches zero,while the flow velocity on the convex ball surface is significantly higher.Additionally,vortices are observed within the flow channel structure,leading to an uneven distribution of electrolyte.Next,modelling is used to optimize the bipolar plate structure of AWE by simulating the electrochemistry and fluid flow performances of four kinds of structures,namely,concave and convex,rhombus,wedge and expanded mesh,in the bipolar plate of alkaline water electrolyzer.The results show that the expanded mesh channel structure has the largest current density of 3330 A/m^(2)and electrolyte flow velocity of 0.507 m/s in the electrolytic cell.Under the same current density,the electrolytic cell with the expanded mesh runner structure has the smallest potential and energy consumption.This work provides a useful guide for the comprehensive understanding and optimization of channel structures,and a theoretical basis for the design of large-scale electrolyzer.
基金supported by the Jilin Province Higher Education TeachingReform Research Project Funding(Contract No.2020285O73B005E).
文摘In the existing power system with a large-scale hydrogen storage system,there are problems such as low efficiency of electric-hydrogen-electricity conversion and single modeling of the hydrogen storage system.In order to improve the hydrogen utilization rate of hydrogen storage system in the process of participating in the power grid operation,and speed up the process of electric-hydrogen-electricity conversion.This article provides a detailed introduction to the mathematical and electrical models of various components of the hydrogen storage unit,and also establishes a charging and discharging efficiency model that considers the temperature and internal gas partial pressure of the hydrogen storage unit.These models are of great significance for studying and optimizing gas storage technology.Through these models,the performance of gas storage units can be better understood and improved.These studies are very helpful for improving energy storage efficiency and sustainable development.The factors affecting the charge-discharge efficiency of hydrogen storage units are analyzed.By integrating the models of each unit and considering the capacity degradation of the hydrogen storage system,we can construct an efficiency model for a large hydrogen storage system and power conversion system.In addition,the simulation models of the hydrogen production system and hydrogen consumption system were established in MATLAB/Simulink.The accuracy and effectiveness of the simulation model were proved by comparing the output voltage variation curve of the simulation with the polarization curve of the typical hydrogen production system and hydrogen consumption system.The results show that the charge-discharge efficiency of the hydrogen storage unit increases with the increase of operating temperature,and H2 and O2 partial voltage have little influence on the charge-discharge efficiency.In the process of power conversion system converter rectification operation,its efficiency decreases with the increase of temperature,while in the process of inverter operation,power conversion system efficiency increases with the increase of temperature.Combined with the efficiency of each hydrogen storage unit and power conversion system converter,the upper limit of the capacity loss of different hydrogen storage units was set.The optimal charge-discharge efficiency of the hydrogen storage system was obtained by using the Cplex solver at 36.46%and 66.34%.
基金supported by the Key Technology Research and Application Demonstration Project for Large-Scale Multi-Scenario Water Electrolysis Hydrogen Production(CTGTC/2023-LQ-06).
文摘The rise in hydrogen production powered by renewable energy is driving the field toward the adoption of systems comprising multiple alkaline water electrolyzers.These setups present various operational modes:independent operation and multi-electrolyzer parallelization,each with distinct advantages and challenges.This study introduces an innovative configuration that incorporates a mutual lye mixer among electrolyzers,establishing a weakly coupled system that combines the advantages of two modes.This approach enables efficient heat utilization for faster hot-startup and maintains heat conservation post-lye interconnection,while preserving the option for independent operation after decoupling.A specialized thermal exchange model is developed for this topology,according to the dynamics of the lye mixer.The study further details startup procedures and proposes optimized control strategies tailored to this structural design.Waste heat from the caustic fully heats up the multiple electrolyzers connected to the lye mixing system,enabling a rapid hot start to enhance the system’s ability to track renewable energy.A control strategy is established to reduce heat loss and increase startup speed,and the optimal valve openings of the diverter valve and the manifold valve are determined.Simulation results indicate a considerable enhancement in operational efficiency,marked by an 18.28%improvement in startup speed and a 6.11%reduction in startup energy consumption inmulti-electrolyzer cluster systems,particularlywhen the systems are synchronized with photovoltaic energy sources.The findings represent a significant stride toward efficient and sustainable hydrogen production,offering a promising path for large-scale integration of renewable energy.
基金the support provided by the Deanship of Scientific Research at Majmaah University,P.O.Box 66,Majmaah 11952,Saudi Arabia under Project No.R-2023-6Center for Refining and Advanced Chemicals,Research Institute,King Fahd University of Petroleum and Minerals(KFUPM),Saudi Arabia。
文摘Hydrogen has been regarded as a promising renewable and green energy source to meet energy needs and attain net-zero carbon emissions.The electrolysis of seawater to make hydrogen is one of the fascinating developments of the twenty-first century.This method uses abundant and relatively inexpensive seawater,as opposed to freshwater,which is rare and can be prohibitively expensive.In recent years,significant research and advancements have been made in direct seawater electrolysis technology for hydrogen production.However,producing highly effective and efficient electrocatalysts with long-term viability under harsh corrosive conditions remains a challenging and severe topic for large-scale seawater electrolysis technology.There is still a large accomplishment gap in understanding how to improve seawater electrolysis to increase hydrogen yields and prolong stability.It is,therefore,crucial to have a condensed knowledge of the tunable and inherent interactions between various electrocatalysts,covering electrolyzer types and paying particular attention to those with high efficiency,chemical stability,and conductivity.The extensive discussion is structured into a progression from noble metals to base metal compounds such as oxides,alloys,phosphides,chalcogenides,hydroxides,and nitrides,MXene-based complexes with a concise examination of hybrid electrocatalysts.In addition,proton exchange membranes,anion exchange membranes,alkaline water electrolyzers,and high-temperature water electrolyzers were potential contributors to seawater’s electrolysis.An extensive assessment of the techno-feasibility,economic insights,and future suggestions was done to commercialize the most efficient electrocatalytic systems for hydrogen production.This review is anticipated to provide academics,environmentalists,and industrial researchers with valuable ideas for constructing and modifying seawater-based electrocatalysts.
基金King Abdullah University of Science and Technology for funding through the funding grant (BAS/1/1413-01-01)the Engineering and Physical Sciences Research Council (EPSRC,EP/V027433/1)+1 种基金the Royal Society (RGSR1211080IESR2212115)。
文摘Electrocatalytic splitting of water by means of renewable energy as the electricity supply is one of the most promising methods for storing green renewable energy as hydrogen. Although two-thirds of the earth’s surface is covered with water, there is inadequacy of freshwater in most parts of the world. Hence, splitting seawater instead of freshwater could be a truly sustainable alternative. However, direct seawater splitting faces challenges because of the complex composition of seawater. The composition, and hence, the local chemistry of seawater may vary depending on its origin, and in most cases, tracking of the side reactions and standardizing and customizing the catalytic process will be an extra challenge. The corrosion of catalysts and competitive side reactions due to the presence of various inorganic and organic pollutants create challenges for developing stable electro-catalysts. Hence, seawater splitting generally involves a two-step process, i.e., purification of seawater using reverse osmosis and then subsequent fresh water splitting. However, this demands two separate chambers and larger space, and increases complexity of the reactor design. Recently, there have been efforts to directly split seawater without the reverse osmosis step. Herein, we represent the most recent innovative approaches to avoid the two-step process, and compare the potential application of membrane-assisted and membrane-less electrolyzers in direct seawater splitting(DSS). We particularly discuss the device engineering, and propose a novel electrolyzer design strategies for concentration gradient based membrane-less microfluidic electrolyzer.
基金National Natural Science Foundation of China(Nos.52071231,51722103)the Natural Science Foundation of Tianjin(No.19JCJQJC61900)。
文摘Anion exchange membrane(AEM)electrolysis is a promising membrane-based green hydrogen production technology.However,AEM electrolysis still remains in its infancy,and the performance of AEM electrolyzers is far behind that of well-developed alkaline and proton exchange membrane electrolyzers.Therefore,breaking through the technical barriers of AEM electrolyzers is critical.On the basis of the analysis of the electrochemical performance tested in a single cell,electrochemical impedance spectroscopy,and the number of active sites,we evaluated the main technical factors that affect AEM electrolyzers.These factors included catalyst layer manufacturing(e.g.,catalyst,carbon black,and anionic ionomer)loadings,membrane electrode assembly,and testing conditions(e.g.,the KOH concentration in the electrolyte,electrolyte feeding mode,and operating temperature).The underlying mechanisms of the effects of these factors on AEM electrolyzer performance were also revealed.The irreversible voltage loss in the AEM electrolyzer was concluded to be mainly associated with the kinetics of the electrode reaction and the transport of electrons,ions,and gas-phase products involved in electrolysis.Based on the study results,the performance and stability of AEM electrolyzers were significantly improved.
基金supported by the National Key Research and Development Program of China(Materials and Process Basis of Electrolytic Hydrogen Production from Fluctuating Power Sources such as Photovoltaic/Wind Power,No.2021YFB4000100)。
文摘To analyze the additional cost caused by the performance attenuation of a proton exchange membrane electrolyzer(PEMEL)under the fluctuating input of renewable energy,this study proposes an optimization method for power scheduling in hydrogen production systems under the scenario of photovoltaic(PV)electrolysis of water.First,voltage and performance attenuation models of the PEMEL are proposed,and the degradation cost of the electrolyzer under a fluctuating input is considered.Then,the calculation of the investment and operating costs of the hydrogen production system for a typical day is based on the life cycle cost.Finally,a layered power scheduling optimization method is proposed to reasonably distribute the power of the electrolyzer and energy storage system in a hydrogen production system.In the up-layer optimization,the PV power absorbed by the hydrogen production system was optimized using MALTAB+Gurobi.In low-layer optimization,the power allocation between the PEMEL and battery energy storage system(BESS)is optimized using a non-dominated sorting genetic algorithm(NSGA-Ⅱ)combined with the firefly algorithm(FA).A better optimization result,characterized by lower degradation and total costs,was obtained using the method proposed in this study.The improved algorithm can search for a better population and obtain optimization results in fewer iterations.As a calculation example,data from a PV power station in northwest China were used for optimization,and the effectiveness and rationality of the proposed optimization method were verified.
基金This work was financially supported by grants from the National Key Research and Development Program of China(2021YFA1501504)Natural Science Foundation of China(22172135,22288102,92045302,and 22021001).
文摘Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realize the storage of renewable energy,for it guarantees the production of value-added chemicals and fuels.Among CO_(2)RR products,formic acid shows great advantages in low energy consumption and high added-value,and thus producing formic acid is generally considered as a profitable line for CO_(2)RR.Bismuth-based electrocatalysts exhibit high formic acid selectivity in CO_(2)RR.Herein,we review the recent progress in bismuth-based electrocatalysts for CO_(2)RR,including material synthesis,performance optimization/validation,and electrolyzers.The effects of morphologies,structure,and composition of bismuth-based electrocatalysts on CO_(2)RR performance are highlighted.Simultaneously,in situ spectroscopic characterization and DFT calculations for reaction mechanism of CO_(2)RR on Bi-based catalysts are emphasized.The applications and optimization of electrolyzers with high current density for CO_(2)RR are summarized.Finally,conclusions and future directions in this field are prospected.
基金supported by National Key R&D Program of China(2020YFA0710200)the National Natural Science Foundation of China(21838010,22122814)+2 种基金the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2018064)State Key Laboratory of Multiphase complex systems,Institute of Process Engineering,Chinese Academy of Sciences(No.MPCS-2022-A-03)Innovation Academy for Green Manufacture Institute,Chinese Academy of Science(IAGM2020C14).
文摘CO_(2) electroreduction(CO_(2) ER)to high value-added chemicals is considered as a promising technology to achieve sustainable carbon neutralization.By virtue of the progressive research in recent years aiming at design and understanding of catalytic materials and electrolyte systems,the CO_(2) ER performance(such as current density,selectivity,stability,CO_(2) conversion,etc.)has been continually increased.Unfortunately,there has been relatively little attention paid to the large-scale CO 2 electrolyzers,which stand just as one obstacle,alongside series-parallel integration,challenging the practical application of this infant technology.In this review,the latest progress on the structures of low-temperature CO_(2) electrolyzers and scale-up studies was systematically overviewed.The influence of the CO_(2) electrolyzer configurations,such as the flow channel design,gas diffusion electrode(GDE)and ion exchange membrane(IEM),on the CO_(2) ER performance was further discussed.The review could provide inspiration for the design of large-scale CO_(2) electrolyzers so as to accelerate the industrial application of CO_(2) ER technology.
基金Financial support from the China Scholarship Council(201806220068,201806650009) to F.Dthe Villum Experiment(grant No.35844) to X.X.
文摘Prussian blue analogues(PBAs) with inherent ordered structures and abundant metal ion sites are widely explored as precursors for various electrochemical applications,including oxygen evolution reaction(OER).Using a range of characterization techniques including Fourier-transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and energy dispersive spectroscopy(EDS),this work discloses the process of replacement of K^(+)by NH4^(+)in the interstitial spaces of the CoFe PBA by a hot aqueous urea solution,which influences the transformation of PBAs under further heat treatment and the OER performance of the deriva tives.After heat treatment at 400℃ under Ar flow,high-resolution transmission electron microscopy(HRTEM) images reveal that CoFe alloy nanoparticles grew on the crystalline cubes of CoFe PBA with K^(+),while CoFe PBA cubes with NH4^(+)become amorphous.Besides,the derivative of CoFe PBA with NH4^(+)(Ar-U-CoFe PBA) performs better than the derivative of CoFe PBA with K^(+)(Ar-CoFe PBA) in OER,registering a lower overpotential of 305 mV at 10 mA cm^(-2),a smaller Tafel slope of 36.1 mV dec^(-1),and better stability over a testing course of 20 h in 1.0 M KOH.A single-cell alkaline electrolyzer,using Ar-U-CoFe PBA and Pt/C for the anodic and cathodic catalyst,respectively,requires an initial cell voltage of 1.66 V to achieve 100 mA cm^(-2)at 80℃,with negligible degradation after100 h.
