By collecting and organizing historical data and typical model characteristics,hydrogen energy storage system(HESS)-based power-to-gas(P2G)and gas-to-power systems are developed using Simulink.The energy transfer mech...By collecting and organizing historical data and typical model characteristics,hydrogen energy storage system(HESS)-based power-to-gas(P2G)and gas-to-power systems are developed using Simulink.The energy transfer mechanisms and numerical modeling methods of the proposed systems are studied in detail.The proposed integrated HESS model covers the following system components:alkaline electrolyzer(AE),highpressure hydrogen storage tank with compressor(CM&H_(2) tank),and proton-exchange membrane fuel cell(PEMFC)stack.The unit models in the HESS are established based on typical U-I curves and equivalent circuit models,which are used to analyze the operating characteristics and charging/discharging behaviors of a typical AE,an ideal CM&H_(2) tank,and a PEMFC stack.The validities of these models are simulated and verified in the MicroGrid system,which is equipped with a wind power generation system,a photovoltaic power generation system,and an auxiliary battery energy storage system(BESS)unit.Simulation results in MATLAB/Simulink show that electrolyzer stack,fuel cell stack and system integration model can operate in different cases.By testing the simulation results of the HESS under different working conditions,the hydrogen production flow,stack voltage,state of charge(SOC)of the BESS,state of hydrogen pressure(SOHP)of the HESS,and HESS energy flow paths are analyzed.The simulation results are consistent with expectations,showing that the integrated HESS model can effectively absorb wind and photovoltaic power.As the wind and photovoltaic power generations increase,the HESS current increases,thereby increasing the amount of hydrogen production to absorb the surplus power.The results show that the HESS responds faster than the traditional BESS in the microgrid,providing a solid theoretical foundation for later wind-photovoltaic-HESS-BESS integration.展开更多
As the most desirable hydrogen production device,the highly efficient acidic proton exchange membrane water electrolyzers(PEMWE)are severely limited by the sluggish kinetics of oxygen evolution reaction(OER)at the ano...As the most desirable hydrogen production device,the highly efficient acidic proton exchange membrane water electrolyzers(PEMWE)are severely limited by the sluggish kinetics of oxygen evolution reaction(OER)at the anode.Rutile IrO2 is a commercial acid-stable OER catalyst with poor activity and high cost,which has motivated the development of alternatives.However,hitherto most of the designed acidic OER catalysts have disadvantages of low activity or stability,which cannot meet the requirement of industrial applications.Thus,exploring suitable strategies to enhance the activity and stability of cost-effective acidic OER catalysts is crucial for developing the PEMWE technique.In this review,the main OER mechanisms,different types of catalysts,and their activity and stability characteristics are summarized and discussed,and then possible strategies to improve activity and stability are proposed.Finally,the problems and prospects of such catalysts are generalized to shed some light on the future research of advanced catalysts for acidic OER.展开更多
Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,t...Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,the anion exchange membrane(AEM) water electrolysis has gained intensive attention and is considered as the next-generation emerging technology due to its potential advantages,such as the use of low-cost non-noble metal catalysts,the relatively mature stack assembly process,etc.However,the AEM water electrolyzer is still in the early development stage of the kW-level stack,which is mainly attributed to severe performance decay caused by the core component,i.e.,AEM.Here,the review comprehensively presents the recent progress of advanced AEM from the view of the performance of water electrolysis cells.Herein,fundamental principles and critical components of AEM water electrolyzers are introduced,and work conditions of AEM water electrolyzers and AEM performance improvement strategies are discussed.The challenges and perspectives are also analyzed.展开更多
Proton exchange membrane fuel cells(PEMFCs)have received a sustained world-wide attention owing to their promising applications based on clean energy.However,their widespread applications are still restricted by the s...Proton exchange membrane fuel cells(PEMFCs)have received a sustained world-wide attention owing to their promising applications based on clean energy.However,their widespread applications are still restricted by the sluggish oxygen reduction reaction(ORR)process.Over the past decades,significant efforts have been devoted to developing efficient ORR catalysts,which have been summarized in numerous previous reviews.Unfortunately,most of them mainly focused on ORR activity on the rotating disk electrode(RDE)level,which cannot truly represent the performance in real applications.Developing and showcasing efficient catalysts evaluated at the membrane electrode assembly(MEA)level is of vital importance.In this review,we first briefly showcased the recent development of ORR catalysts and then put more emphasis on the discussion of designing efficient catalysts at MEA and full-cell level,aiming to help stimulate more attention on their practical applications.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
The efficiency of proton exchange membrane water electrolysis(PEM-WE)for hydrogen production is heavily dependent on the noble metal iridium-based catalysts.However,the scarcity of iridium limits the large-scale appli...The efficiency of proton exchange membrane water electrolysis(PEM-WE)for hydrogen production is heavily dependent on the noble metal iridium-based catalysts.However,the scarcity of iridium limits the large-scale application of PEM-WE.To address this issue,it is promising to select an appropriate support because it not only enhances the utilization efficiency of noble metals but also improves mass transport under high current.Herein,we supported amorphous IrO_(x) nanosheets onto the hollow TiO_(2) sphere(denoted as IrO_(x)),which demonstrated excellent performance in acidic electrolytic water splitting.Specifically,the annealed IrO_(x)catalyst at 150℃in air exhibited a mass activity of 1347.5 A·gIr^(−1),which is much higher than that of commercial IrO_(2) of 12.33 A·gIr^(−1) at the overpotential of 300 mV for oxygen evolution reaction(OER).Meanwhile,the annealed IrO_(x) exhibited good stability for 600 h operating at 10 mA·cm^(−2).Moreover,when using IrO_(x) and annealed IrO_(x) catalysts for water splitting,a cell voltage as low as 1.485 V can be achieved at 10 mA·cm^(−2).The cell can continuously operate for 200 h with negligible degradation of performance.展开更多
The sluggish reaction kinetics of alkaline hydrogen oxidation reaction(HOR)is one of the key challenges for anion exchange membrane fuel cells(AEMFCs).To achieve robust alkaline HOR with minimized cost,we developed a ...The sluggish reaction kinetics of alkaline hydrogen oxidation reaction(HOR)is one of the key challenges for anion exchange membrane fuel cells(AEMFCs).To achieve robust alkaline HOR with minimized cost,we developed a single atom-cluster multiscale structure with isolated Pt single atoms anchored on Ru nanoclusters supported on nitrogen-doped carbon nanosheets(Pt1-Ru/NC).The well-defined structure not only provides multiple sites with varied affinity with the intermediates but also enables simultaneous modulation of different sites via interfacial interaction.In addition to weakening Ru–H bond strength,the isolated Pt sites are heavily involved in hydrogen adsorption and synergistically accelerate the Volmer step with the help of Ru sites.Furthermore,this catalyst configuration inhibits the excessive occupancy of oxygen-containing species on Ru sites and facilitates the HOR at elevated potentials.The Pt1-Ru/NC catalyst exhibits superior alkaline HOR performance with extremely high activity and excellent CO-tolerance.An AEMFC with a 0.1 mg·cmPGM^(−2)loading of Pt1-Ru/NC anode catalyst achieves a peak powder density of 1172 mW·cm^(−2),which is 2.17 and 1.55 times higher than that of Pt/C and PtRu/C,respectively.This work provides a new catalyst concept to address the sluggish kinetics of electrocatalytic reactions containing multiple intermediates and elemental steps.展开更多
Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to...Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to obtain high-purity hydrogen.Nevertheless,electrocatalysts used in the process are fabricated using conventional wet chemical synthesis methods,such as sol-gel,hydrothermal,or surfactantassisted approaches,which often necessitate intricate pretreatment procedures and are vulnerable to post-treatment contamination.Therefore,this study introduces a streamlined and environmentally conscious one-step potential-cycling approach to generate a highly efficient trimetallic nickel-iron-copper electrocatalyst in situ on nickel foam.The synthesized material exhibited remarkable performance,requiring a mere 476 mV to drive electrochemical water splitting at 100 mA cm^(-2)current density in alkaline solution.Furthermore,this material was integrated into an anion exchange membrane watersplitting device and achieved an exceptionally high current density of 1 A cm^(-2)at a low cell voltage of2.13 V,outperforming the noble-metal benchmark(2.51 V).Additionally,ex situ characterizations were employed to detect transformations in the active sites during the catalytic process,revealing the structural transformations and providing inspiration for further design of electrocatalysts.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
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
We report herein a visible light-mediated direct deuteration of alkenes with D_(2)O or deuterated methanol(MeOD)using a cobaloxime as a hydrogen/deuterium(H/D)exchange catalyst.The synergistic photoredox/Co catalysis ...We report herein a visible light-mediated direct deuteration of alkenes with D_(2)O or deuterated methanol(MeOD)using a cobaloxime as a hydrogen/deuterium(H/D)exchange catalyst.The synergistic photoredox/Co catalysis enabled facile deuterium(D)-incorporation of a variety of terminal and internal alkenes at either terminal or benzylic positions.We proposed that this process proceeded through a sequence of reversible addition-elimination reactions and fast proton exchange involving Co(III)–H,which was generated in situ by photoreduction.展开更多
Peptides can be potentmolecules with high efficacy and selectivity in the development of biotherapeutics.However,the poor pharmacokinetic properties of peptides pose major challenges for their broader medicinal applic...Peptides can be potentmolecules with high efficacy and selectivity in the development of biotherapeutics.However,the poor pharmacokinetic properties of peptides pose major challenges for their broader medicinal applications.Inspired by the proteinstabilizing role of natural N-glycosylation,we design and synthesize a series of parathyroid hormone(PTH)peptides(1-34),bearing either N-GlcNAc or biantennary complex-type N-glycan modification,and evaluate their serum stability and biological activities.The results indicate that an N-Asn-linked complex-type sialylundecasaccharide can increase the serum half-life and in vivo bioactivity of PTH peptides with a broad tolerance of modification sites.Further,hydrogen/deuterium exchange mass spectroscopy indicates that the larger-sized Nglycan can induce enhanced hydration dynamics in its surroundings,which may facilitate an improved resistance for the peptide against enzymatic proteolysis.This sialylundecasaccharide-based peptideengineering strategy has also been applied to glucagon-like peptide-1(7-37),leading to glycopeptides with enhanced hypoglycemic activity and acting time in vivo.Together,these results demonstrate the potential of using sialylated complextype N-glycan as a general engineering strategy for developing long-acting peptide therapeutics.展开更多
Transition metal sulfides with homogeneous multi-metallic elements promise high catalytic performance for water electrolysis owing to the unique structure and highly tailorable electrochemical property.Most existing s...Transition metal sulfides with homogeneous multi-metallic elements promise high catalytic performance for water electrolysis owing to the unique structure and highly tailorable electrochemical property.Most existing synthetic routes require high temperature to ensure the uniform mixing of various elements,making the synthesis highly challenging.Here,for the first-time novel carbon fiber supported high-entropy Co-Zn-Cd-Cu-Mn sulfide(CoZnCdCuMnS@CF)nanoarrays are fabricated by the mild cation exchange strategy.Benefiting from the synergistic effect among multiple metals and the strong interfacial bonding between high-entropy Co-Zn-Cd-Cu-Mn sulfide nanoarrays and the carbon fiber support,CoZnCdCuMnS@CF exhibits superior catalytic activity and stability toward overall water splitting in alkaline medium.Impressively,CoZnCdCuMnS@CF only needs low overpotentials of 173 and 220 mV to reach the current density of 10 mA•cm^(−2),with excellent durability for over 70 and 113 h for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)respectively.More importantly,the bifunctional electrode(CoZnCdCuMnS@CF||CoZnCdCuMnS@CF)for overall water splitting can deliver a small cell voltage of 1.63 V to afford 10 mA•cm^(−2) and exhibit outstanding stability of negligible decay after 73 h continuous operation.This work provides a viable synthesis route toward advanced high-entropy materials with great potential applications.展开更多
Jasmonates(JAs)are plant hormones with crucial roles in development and stress resilience.They activate MYC transcription factors by mediating the proteolysis of MYC inhibitors called JAZ proteins.In the absence of JA...Jasmonates(JAs)are plant hormones with crucial roles in development and stress resilience.They activate MYC transcription factors by mediating the proteolysis of MYC inhibitors called JAZ proteins.In the absence of JA,JAZ proteins bind and inhibit MYC through the assembly of MYC–JAZ–Novel Interactor of JAZ(NINJA)–TPL repressor complexes.However,JAZ and NINJA are predicted to be largely intrinsically unstructured,which has precluded their experimental structure determination.Through a combination of biochemical,mutational,and biophysical analyses and AlphaFold-derived ColabFold modeling,we characterized JAZ–JAZ and JAZ–NINJA interactions and generated models with detailed,high-confidence domain interfaces.We demonstrate that JAZ,NINJA,and MYC interface domains are dynamic in isolation and become stabilized in a stepwise order upon complex assembly.By contrast,most JAZ and NINJA regions outside of the interfaces remain highly dynamic and cannot be modeled in a single conformation.Our data indicate that the small JAZ Zinc finger expressed in Inflorescence Meristem(ZIM)motif mediates JAZ–JAZ and JAZ–NINJA interactions through separate surfaces,and our data further suggest that NINJA modulates JAZ dimerization.This study advances our understanding of JA signaling by providing insights into the dynamics,interactions,and structure of the JAZ–NINJA core of the JA repressor complex.展开更多
LiBH_(4) has been considered as one of the most promising energy storage materials with its ultrahigh hydrogen capacity,which can supply hydrogen through hydrolysis process or realize hydrogen-to-electricity conversio...LiBH_(4) has been considered as one of the most promising energy storage materials with its ultrahigh hydrogen capacity,which can supply hydrogen through hydrolysis process or realize hydrogen-to-electricity conversion via anodic oxidation reaction of direct borohydride fuel cells(DBFCs).However,the realization of practical hydrogen applications heavily depends on the effective synthesis of high-purity LiBH_(4) and recycling of the spent fuels(LiBO_(2)·xH_(2)O).The present work demonstrates a convenient and high-efficiency solvent-free strategy for regenerating LiBH_(4) with a maximum yield close to 80%,by retrieving its by-products with MgH_(2) as a reducing agent under ambient conditions.Besides,the hydrogen released from the regeneration course can completely compensate the demand for consumed MgH_(2).The isotopic tracer method reveals that the hydrogen stored in LiBH_(4) comes from both MgH_(2) and coordinated water bound to LiBO_(2).Here,the expensive MgH_(2) can be substituted with the readily available and cost-effective MgH_(2)-Mg mixtures to simplify the regeneration route.Notably,LiBH_(4) catalyzed by CoCl_(2) can stably supply hydrogen to proton exchange membrane fuel cell(PEMFC),thus powering a portable prototype vehicle.By combining hydrogen storage,production and utilization in a closed cycle,this work offers new insights into deploying boron-based hydrides for energy applications.展开更多
Uridine diphosphate-dependent glycosyltransferases(UGTs)mediate the glycosylation of plant metabolites,thereby altering their physicochemical properties and bioactivities.Plants possess numerous UGT genes,with the enc...Uridine diphosphate-dependent glycosyltransferases(UGTs)mediate the glycosylation of plant metabolites,thereby altering their physicochemical properties and bioactivities.Plants possess numerous UGT genes,with the encoded enzymes often glycosylating multiple substrates and some exhibiting substrate inhibition kinetics,but the biological function and molecular basis of these phenomena are not fully understood.The promiscuous monolignol/phytoalexin glycosyltransferase NbUGT72AY1 exhibits substrate inhibition(Ki)at 4 mM scopoletin,whereas the highly homologous monolignol StUGT72AY2 is inhibited at 190 mM.We therefore used hydrogen/deuterium exchange mass spectrometry and structure-based mutational analyses of both proteins and introduced NbUGT72AY1 residues into StUGT72AY2 and vice versa to study promiscuity and substrate inhibition of UGTs.A single F87I and chimeric mutant of NbUGT72AY1 showed significantly reducedscopoletin substrate inhibition,whereas its monolignolgly cosylation activity was almost unaffected.Reverse mutations in StUGT72AY2 resulted in increased scopoletin glycosylation,leading to enhanced promiscuity,which was accompanied by substrate inhibition.Studies of 3D structures identified open and closed UGT conformers,allowing visualization of the dynamics of conformational changes that occur during catalysis.Previously postulated substrate access tunnels likely serve as drainage channels.The results suggest a two-site model in which the second substrate molecule binds near the catalytic site and blocks product release.Mutational studies showed that minor changes in amino acid sequence can enhance the promiscuity of the enzyme and add new capabilities such as substrate inhibition without affecting existing functions.The proposed subfunctionalization mechanism of expanded promiscuity may play a role in enzyme evolution and highlights the importance of promiscuous enzymes in providing new functions.展开更多
基金supported by the State Grid Jiangxi Electric Power Co.,Ltd.(No.52182020008K)Beijing Millions of Talents Funding Project(No.2020A30).
文摘By collecting and organizing historical data and typical model characteristics,hydrogen energy storage system(HESS)-based power-to-gas(P2G)and gas-to-power systems are developed using Simulink.The energy transfer mechanisms and numerical modeling methods of the proposed systems are studied in detail.The proposed integrated HESS model covers the following system components:alkaline electrolyzer(AE),highpressure hydrogen storage tank with compressor(CM&H_(2) tank),and proton-exchange membrane fuel cell(PEMFC)stack.The unit models in the HESS are established based on typical U-I curves and equivalent circuit models,which are used to analyze the operating characteristics and charging/discharging behaviors of a typical AE,an ideal CM&H_(2) tank,and a PEMFC stack.The validities of these models are simulated and verified in the MicroGrid system,which is equipped with a wind power generation system,a photovoltaic power generation system,and an auxiliary battery energy storage system(BESS)unit.Simulation results in MATLAB/Simulink show that electrolyzer stack,fuel cell stack and system integration model can operate in different cases.By testing the simulation results of the HESS under different working conditions,the hydrogen production flow,stack voltage,state of charge(SOC)of the BESS,state of hydrogen pressure(SOHP)of the HESS,and HESS energy flow paths are analyzed.The simulation results are consistent with expectations,showing that the integrated HESS model can effectively absorb wind and photovoltaic power.As the wind and photovoltaic power generations increase,the HESS current increases,thereby increasing the amount of hydrogen production to absorb the surplus power.The results show that the HESS responds faster than the traditional BESS in the microgrid,providing a solid theoretical foundation for later wind-photovoltaic-HESS-BESS integration.
基金State Key Laboratory of Advanced Technology for Materials Synthesisand Processing,Grant/AwardNumber:2022-ZD-4National Natural Science Foundation of China,Grant/Award Numbers:22075223,22179104。
文摘As the most desirable hydrogen production device,the highly efficient acidic proton exchange membrane water electrolyzers(PEMWE)are severely limited by the sluggish kinetics of oxygen evolution reaction(OER)at the anode.Rutile IrO2 is a commercial acid-stable OER catalyst with poor activity and high cost,which has motivated the development of alternatives.However,hitherto most of the designed acidic OER catalysts have disadvantages of low activity or stability,which cannot meet the requirement of industrial applications.Thus,exploring suitable strategies to enhance the activity and stability of cost-effective acidic OER catalysts is crucial for developing the PEMWE technique.In this review,the main OER mechanisms,different types of catalysts,and their activity and stability characteristics are summarized and discussed,and then possible strategies to improve activity and stability are proposed.Finally,the problems and prospects of such catalysts are generalized to shed some light on the future research of advanced catalysts for acidic OER.
基金supported by the National Key Research and Development Program(2022YFB4202200)the Fundamental Research Funds for the Central Universities and sponsored by Shanghai Pujiang Program(22PJ1413100)。
文摘Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,the anion exchange membrane(AEM) water electrolysis has gained intensive attention and is considered as the next-generation emerging technology due to its potential advantages,such as the use of low-cost non-noble metal catalysts,the relatively mature stack assembly process,etc.However,the AEM water electrolyzer is still in the early development stage of the kW-level stack,which is mainly attributed to severe performance decay caused by the core component,i.e.,AEM.Here,the review comprehensively presents the recent progress of advanced AEM from the view of the performance of water electrolysis cells.Herein,fundamental principles and critical components of AEM water electrolyzers are introduced,and work conditions of AEM water electrolyzers and AEM performance improvement strategies are discussed.The challenges and perspectives are also analyzed.
基金support by the Natural Science Foundation of Shandong Province(No.ZR202103040753)the National Natural Science Foundation of China(No.22102086).
文摘Proton exchange membrane fuel cells(PEMFCs)have received a sustained world-wide attention owing to their promising applications based on clean energy.However,their widespread applications are still restricted by the sluggish oxygen reduction reaction(ORR)process.Over the past decades,significant efforts have been devoted to developing efficient ORR catalysts,which have been summarized in numerous previous reviews.Unfortunately,most of them mainly focused on ORR activity on the rotating disk electrode(RDE)level,which cannot truly represent the performance in real applications.Developing and showcasing efficient catalysts evaluated at the membrane electrode assembly(MEA)level is of vital importance.In this review,we first briefly showcased the recent development of ORR catalysts and then put more emphasis on the discussion of designing efficient catalysts at MEA and full-cell level,aiming to help stimulate more attention on their practical applications.
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The National Key R&D Program of China(Nos.2018YFA0702001 and 2021YFA1500400)the National Natural Science Foundation of China(Nos.22371268 and 22175163)+2 种基金Fundamental Research Funds for the Central Universities(No.WK2060000016)Anhui Development and Reform Commission(No.AHZDCYCX-2SDT2023-07)Youth Innovation Promotion Association of the Chinese Academy of Science(No.2018494)supported this work.
文摘The efficiency of proton exchange membrane water electrolysis(PEM-WE)for hydrogen production is heavily dependent on the noble metal iridium-based catalysts.However,the scarcity of iridium limits the large-scale application of PEM-WE.To address this issue,it is promising to select an appropriate support because it not only enhances the utilization efficiency of noble metals but also improves mass transport under high current.Herein,we supported amorphous IrO_(x) nanosheets onto the hollow TiO_(2) sphere(denoted as IrO_(x)),which demonstrated excellent performance in acidic electrolytic water splitting.Specifically,the annealed IrO_(x)catalyst at 150℃in air exhibited a mass activity of 1347.5 A·gIr^(−1),which is much higher than that of commercial IrO_(2) of 12.33 A·gIr^(−1) at the overpotential of 300 mV for oxygen evolution reaction(OER).Meanwhile,the annealed IrO_(x) exhibited good stability for 600 h operating at 10 mA·cm^(−2).Moreover,when using IrO_(x) and annealed IrO_(x) catalysts for water splitting,a cell voltage as low as 1.485 V can be achieved at 10 mA·cm^(−2).The cell can continuously operate for 200 h with negligible degradation of performance.
基金financially supported by the National Natural Science Foundation of China(Nos.52171224 and 92261119)J.M.W.acknowledges support from Zhejiang Province Postdoctoral Science Foundation(No.ZJ2022003)China Postdoctoral Science Foundation(No.2023M733020).
文摘The sluggish reaction kinetics of alkaline hydrogen oxidation reaction(HOR)is one of the key challenges for anion exchange membrane fuel cells(AEMFCs).To achieve robust alkaline HOR with minimized cost,we developed a single atom-cluster multiscale structure with isolated Pt single atoms anchored on Ru nanoclusters supported on nitrogen-doped carbon nanosheets(Pt1-Ru/NC).The well-defined structure not only provides multiple sites with varied affinity with the intermediates but also enables simultaneous modulation of different sites via interfacial interaction.In addition to weakening Ru–H bond strength,the isolated Pt sites are heavily involved in hydrogen adsorption and synergistically accelerate the Volmer step with the help of Ru sites.Furthermore,this catalyst configuration inhibits the excessive occupancy of oxygen-containing species on Ru sites and facilitates the HOR at elevated potentials.The Pt1-Ru/NC catalyst exhibits superior alkaline HOR performance with extremely high activity and excellent CO-tolerance.An AEMFC with a 0.1 mg·cmPGM^(−2)loading of Pt1-Ru/NC anode catalyst achieves a peak powder density of 1172 mW·cm^(−2),which is 2.17 and 1.55 times higher than that of Pt/C and PtRu/C,respectively.This work provides a new catalyst concept to address the sluggish kinetics of electrocatalytic reactions containing multiple intermediates and elemental steps.
基金financially supported by the National Natural Science Foundation of China(21975100).
文摘Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to obtain high-purity hydrogen.Nevertheless,electrocatalysts used in the process are fabricated using conventional wet chemical synthesis methods,such as sol-gel,hydrothermal,or surfactantassisted approaches,which often necessitate intricate pretreatment procedures and are vulnerable to post-treatment contamination.Therefore,this study introduces a streamlined and environmentally conscious one-step potential-cycling approach to generate a highly efficient trimetallic nickel-iron-copper electrocatalyst in situ on nickel foam.The synthesized material exhibited remarkable performance,requiring a mere 476 mV to drive electrochemical water splitting at 100 mA cm^(-2)current density in alkaline solution.Furthermore,this material was integrated into an anion exchange membrane watersplitting device and achieved an exceptionally high current density of 1 A cm^(-2)at a low cell voltage of2.13 V,outperforming the noble-metal benchmark(2.51 V).Additionally,ex situ characterizations were employed to detect transformations in the active sites during the catalytic process,revealing the structural transformations and providing inspiration for further design of electrocatalysts.
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the Natural Science Foundation of China(grant nos.91956000,22031006,21861132003),Tsinghua University Initiative Scientific Research Program,and Haihe Laboratory of Sustainable Chemical Transformations for financial support.
文摘We report herein a visible light-mediated direct deuteration of alkenes with D_(2)O or deuterated methanol(MeOD)using a cobaloxime as a hydrogen/deuterium(H/D)exchange catalyst.The synergistic photoredox/Co catalysis enabled facile deuterium(D)-incorporation of a variety of terminal and internal alkenes at either terminal or benzylic positions.We proposed that this process proceeded through a sequence of reversible addition-elimination reactions and fast proton exchange involving Co(III)–H,which was generated in situ by photoreduction.
基金This research was made possible as a result of a generous grant from the Beijing National Science Foundation(grant no.JQ18024)the National Key R&D Program of China(grant no.2018YFA0507602)the National Natural Science Foundation of China(grant nos.91953111 and 91853113).
文摘Peptides can be potentmolecules with high efficacy and selectivity in the development of biotherapeutics.However,the poor pharmacokinetic properties of peptides pose major challenges for their broader medicinal applications.Inspired by the proteinstabilizing role of natural N-glycosylation,we design and synthesize a series of parathyroid hormone(PTH)peptides(1-34),bearing either N-GlcNAc or biantennary complex-type N-glycan modification,and evaluate their serum stability and biological activities.The results indicate that an N-Asn-linked complex-type sialylundecasaccharide can increase the serum half-life and in vivo bioactivity of PTH peptides with a broad tolerance of modification sites.Further,hydrogen/deuterium exchange mass spectroscopy indicates that the larger-sized Nglycan can induce enhanced hydration dynamics in its surroundings,which may facilitate an improved resistance for the peptide against enzymatic proteolysis.This sialylundecasaccharide-based peptideengineering strategy has also been applied to glucagon-like peptide-1(7-37),leading to glycopeptides with enhanced hypoglycemic activity and acting time in vivo.Together,these results demonstrate the potential of using sialylated complextype N-glycan as a general engineering strategy for developing long-acting peptide therapeutics.
基金The authors thank the National Natural Science Foundation of China(No.U1804140)China Postdoctoral Science Foundation(No.2021M702939)for support.
文摘Transition metal sulfides with homogeneous multi-metallic elements promise high catalytic performance for water electrolysis owing to the unique structure and highly tailorable electrochemical property.Most existing synthetic routes require high temperature to ensure the uniform mixing of various elements,making the synthesis highly challenging.Here,for the first-time novel carbon fiber supported high-entropy Co-Zn-Cd-Cu-Mn sulfide(CoZnCdCuMnS@CF)nanoarrays are fabricated by the mild cation exchange strategy.Benefiting from the synergistic effect among multiple metals and the strong interfacial bonding between high-entropy Co-Zn-Cd-Cu-Mn sulfide nanoarrays and the carbon fiber support,CoZnCdCuMnS@CF exhibits superior catalytic activity and stability toward overall water splitting in alkaline medium.Impressively,CoZnCdCuMnS@CF only needs low overpotentials of 173 and 220 mV to reach the current density of 10 mA•cm^(−2),with excellent durability for over 70 and 113 h for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)respectively.More importantly,the bifunctional electrode(CoZnCdCuMnS@CF||CoZnCdCuMnS@CF)for overall water splitting can deliver a small cell voltage of 1.63 V to afford 10 mA•cm^(−2) and exhibit outstanding stability of negligible decay after 73 h continuous operation.This work provides a viable synthesis route toward advanced high-entropy materials with great potential applications.
基金supported by the Van Andel Institute(to K.M.)the National Science Foundation(NSF+6 种基金MCB-1922846 to K.M.)the Six Talent Peaks Project in Jiangsu Province(NY-035 to F.Z.)the Fok Ying Tong Education Foundation(161022 to F.Z.)the National Institutes of Health(grant R01 GM57795 to G.A.H.)the Chemical Sciences,Geosciences,and Biosciences Division,Basic Energy Sciences,Office of Science at the U.S.Department of Energy(grant DE–FG02–91ER20021 to G.A.H.for infrastructure support)the Michigan State University Plant Resilience Institute(for support of L.V.-C.)the Michigan AgBioResearch Project(grant MICL02278 to G.A.H.).
文摘Jasmonates(JAs)are plant hormones with crucial roles in development and stress resilience.They activate MYC transcription factors by mediating the proteolysis of MYC inhibitors called JAZ proteins.In the absence of JA,JAZ proteins bind and inhibit MYC through the assembly of MYC–JAZ–Novel Interactor of JAZ(NINJA)–TPL repressor complexes.However,JAZ and NINJA are predicted to be largely intrinsically unstructured,which has precluded their experimental structure determination.Through a combination of biochemical,mutational,and biophysical analyses and AlphaFold-derived ColabFold modeling,we characterized JAZ–JAZ and JAZ–NINJA interactions and generated models with detailed,high-confidence domain interfaces.We demonstrate that JAZ,NINJA,and MYC interface domains are dynamic in isolation and become stabilized in a stepwise order upon complex assembly.By contrast,most JAZ and NINJA regions outside of the interfaces remain highly dynamic and cannot be modeled in a single conformation.Our data indicate that the small JAZ Zinc finger expressed in Inflorescence Meristem(ZIM)motif mediates JAZ–JAZ and JAZ–NINJA interactions through separate surfaces,and our data further suggest that NINJA modulates JAZ dimerization.This study advances our understanding of JA signaling by providing insights into the dynamics,interactions,and structure of the JAZ–NINJA core of the JA repressor complex.
基金This work was financially supported by the National Natural Science Foundation of China Projects(Nos.51771075)the National Key R&D Program of China(No.2018YFB1502101)+2 种基金the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.NSFC51621001)by the Project Supported by Nat-ural Science Foundation of Guangdong Province of China(2016A030312011)Shao acknowledges support from Macao Science and Technology Development Fund(FDCT)(Project No.:0062/2018/A2 and 0019/2019/AGJ).
文摘LiBH_(4) has been considered as one of the most promising energy storage materials with its ultrahigh hydrogen capacity,which can supply hydrogen through hydrolysis process or realize hydrogen-to-electricity conversion via anodic oxidation reaction of direct borohydride fuel cells(DBFCs).However,the realization of practical hydrogen applications heavily depends on the effective synthesis of high-purity LiBH_(4) and recycling of the spent fuels(LiBO_(2)·xH_(2)O).The present work demonstrates a convenient and high-efficiency solvent-free strategy for regenerating LiBH_(4) with a maximum yield close to 80%,by retrieving its by-products with MgH_(2) as a reducing agent under ambient conditions.Besides,the hydrogen released from the regeneration course can completely compensate the demand for consumed MgH_(2).The isotopic tracer method reveals that the hydrogen stored in LiBH_(4) comes from both MgH_(2) and coordinated water bound to LiBO_(2).Here,the expensive MgH_(2) can be substituted with the readily available and cost-effective MgH_(2)-Mg mixtures to simplify the regeneration route.Notably,LiBH_(4) catalyzed by CoCl_(2) can stably supply hydrogen to proton exchange membrane fuel cell(PEMFC),thus powering a portable prototype vehicle.By combining hydrogen storage,production and utilization in a closed cycle,this work offers new insights into deploying boron-based hydrides for energy applications.
文摘Uridine diphosphate-dependent glycosyltransferases(UGTs)mediate the glycosylation of plant metabolites,thereby altering their physicochemical properties and bioactivities.Plants possess numerous UGT genes,with the encoded enzymes often glycosylating multiple substrates and some exhibiting substrate inhibition kinetics,but the biological function and molecular basis of these phenomena are not fully understood.The promiscuous monolignol/phytoalexin glycosyltransferase NbUGT72AY1 exhibits substrate inhibition(Ki)at 4 mM scopoletin,whereas the highly homologous monolignol StUGT72AY2 is inhibited at 190 mM.We therefore used hydrogen/deuterium exchange mass spectrometry and structure-based mutational analyses of both proteins and introduced NbUGT72AY1 residues into StUGT72AY2 and vice versa to study promiscuity and substrate inhibition of UGTs.A single F87I and chimeric mutant of NbUGT72AY1 showed significantly reducedscopoletin substrate inhibition,whereas its monolignolgly cosylation activity was almost unaffected.Reverse mutations in StUGT72AY2 resulted in increased scopoletin glycosylation,leading to enhanced promiscuity,which was accompanied by substrate inhibition.Studies of 3D structures identified open and closed UGT conformers,allowing visualization of the dynamics of conformational changes that occur during catalysis.Previously postulated substrate access tunnels likely serve as drainage channels.The results suggest a two-site model in which the second substrate molecule binds near the catalytic site and blocks product release.Mutational studies showed that minor changes in amino acid sequence can enhance the promiscuity of the enzyme and add new capabilities such as substrate inhibition without affecting existing functions.The proposed subfunctionalization mechanism of expanded promiscuity may play a role in enzyme evolution and highlights the importance of promiscuous enzymes in providing new functions.
