Water electrolysis poses a significant challenge for balancing catalytic activity and stability of oxygen evolution reaction(OER)electrocatalysts.In this study,we address this challenge by constructing asymmetric redo...Water electrolysis poses a significant challenge for balancing catalytic activity and stability of oxygen evolution reaction(OER)electrocatalysts.In this study,we address this challenge by constructing asymmetric redox chemistry through elaborate surface OO–Ru–OH and bulk Ru–O–Ni/Fe coordination moieties within single-atom Ru-decorated defective NiFe LDH nanosheets(Ru@d-NiFe LDH)in conjunction with strong metal-support interactions(SMSI).Rigorous spectroscopic characterization and theoretical calculations indicate that single-atom Ru can delocalize the O 2p electrons on the surface and optimize d-electron configurations of metal atoms in bulk through SMSI.The^(18)O isotope labeling experiment based on operando differential electrochemical mass spectrometry(DEMS),chemical probe experiments,and theoretical calculations confirm the encouraged surface lattice oxygen,stabilized bulk lattice oxygen,and enhanced adsorption of oxygen-containing intermediates for bulk metals in Ru@d-NiFe LDH,leading to asymmetric redox chemistry for OER.The Ru@d-NiFe LDH electrocatalyst exhibits exceptional performance with an overpotential of 230 mV to achieve 10 mA cm^(−2)and maintains high robustness under industrial current density.This approach for achieving asymmetric redox chemistry through SMSI presents a new avenue for developing high-performance electrocatalysts and instills confidence in its industrial applicability.展开更多
The electrolysis of natural seawater powered by abundant offshore renewable energy is widely considered as a sustainable hydrogen production technique.However,the competitive chlorine evolution reaction severely damag...The electrolysis of natural seawater powered by abundant offshore renewable energy is widely considered as a sustainable hydrogen production technique.However,the competitive chlorine evolution reaction severely damages the catalyst durability in the anodic seawater oxidation.Here,we demonstrate that the in situ chromate cover restructured from a preformed Crbased metal organic framework(MIL-101(Cr))stabilizes anodic seawater oxidation while maintaining high activity on an optimized NiFe-layered double hydroxide(NiFe-LDH)array catalyst.Impressively,such a cover enables an over 20-fold reduction in overpotential attenuation rate(0.11 mV·h^(-1))in comparison to the unmodified NiFe-LDH counterpart(2.38 mV·h^(-1))against a stable 185 h operation.A combination of experiment studies and theoretical calculations has unveiled that the in situ generated chromate cover weaken unfavorable Cl^(-)adsorption more notably over reactive OH−,therefore mitigating the Cl-related corrosion on the NiFe-LDH.The present study advances a stability breakthrough in the feasible implementation of direct seawater electrolysis for sustainable green hydrogen production.展开更多
As the main limiting step of overall water splitting,oxygen evolution reaction(OER)is urgent to be enhanced by developing efficient catalysts to promote the process of electrolytic water.Based on theoretical analysis,...As the main limiting step of overall water splitting,oxygen evolution reaction(OER)is urgent to be enhanced by developing efficient catalysts to promote the process of electrolytic water.Based on theoretical analysis,the Ni-metal-organic framework(Ni-MOF)and NiFe-layered double hydroxide(NiFe-LDH)(NiFe-LDH/MOF)heterostructure can optimize the energy barrier of the OER process and decrease the adsorption energy of oxygen-containing intermediates,effectively accelerating the OER kinetics.Accordingly,layered NiFe-LDH/MOF heterostructures are in situ constructed through a facile two-step reaction process,with substantial oxygen defects and lattice defects that further improve the catalytic performance.As a result,only 208 and 275 mV OER overpotentials are needed for NiFe-LDH/MOF to drive the current densities of 20 and 100 mA·cm^(-2)in 1 M KOH solutions,and even maintain catalytic stability of 100 h at 20 mA·cm^(-2).When applied to seawater oxidation,only 235 and 307 mV OER overpotentials are required to achieve the current densities of 20 and 100 mA·cm^(-2),respectively,with almost no attenuation for 100 h stability test at 20 mA·cm^(-2),all better than commercial RuO_(2).This work provides the theoretical and experimental basis and a new idea for efficiently driving fresh water and seawater cracking by heterostructure and defect coupling design toward catalysts.展开更多
Transition metal-based layered double hydroxides(LDHs)have been capable of working efficiently as catalysts in the basic oxygen evolution reaction(OER)for sustaining hydrogen production of alkaline water electrolysis....Transition metal-based layered double hydroxides(LDHs)have been capable of working efficiently as catalysts in the basic oxygen evolution reaction(OER)for sustaining hydrogen production of alkaline water electrolysis.Nevertheless,exploring new LDH-based electrocatalysts featuring both remarkable activity and good stability is still in high demand,which is pivotal for comprehensive understanding and impressive improvement of the sluggish OER kinetics.Here,a series of bimetallic(Co and Mo)LDH arrays were designed and fabricated via a facile and controlled strategy by incorporating a Mo source into presynthesized Co-based metal-organic framework(MOF)arrays on carbon cloth(CC),named as ZIF-67/CC arrays.We found that tuning the Mo content resulted in gradual differences in the structural properties,surface morphology,and chemical states of the resulting catalysts,namely CoMox-LDH/CC(x representing the added weight of the Mo source).Gratifyingly,the best-performing CoMo_(0.20)-LDH/CC electrocatalyst demonstrates a low overpotential of only 226 mV and high stability at a current density of 10 mA·cm^(−2),which is superior to most LDH-based OER catalysts reported previously.Furthermore,it only required 1.611 V voltage to drive the overall water splitting device at the current density of 10 mA·cm^(−2).The present study represents a significant advancement in the development and applications of new OER catalysts.展开更多
Within the framework of achieving global carbon neutrality,utilizing electrocatalytic water splitting to produce“green hydrogen”holds significant promise as an effective solution.The strategic development of economi...Within the framework of achieving global carbon neutrality,utilizing electrocatalytic water splitting to produce“green hydrogen”holds significant promise as an effective solution.The strategic development of economic,efficient,and robust anode oxygen evolution reaction(OER)catalysts is one of the imminent bottlenecks for scalable application of electrolyzing water into hydrogen and oxygen,particularly under actual yet harsh operating conditions such as large current density(LCD).In this review,we intend to summarize the advances and challenges in the understanding of the electrocatalytic OER at LCD.Initially,the impact of LCD on the electron transfer,mass transportation efficiency and catalyst stability is identified and summarized.Furthermore,five basic principles for catalyst design,namely the dimension of the materials,surface chemistry,creation of electron transfer pathways,synergy among nano-,micro-,and macroscale structures,and catalyst-support interaction,are systematically discussed.Specifically,the correlation between the synergistic function of the multiscale structures and the catalyst-support interaction is highlighted to direct improvements in catalyst efficiency and durability at the LCD.Finally,an outlook is prospected to further our understanding of these topics and provide related researchers with potential research areas.展开更多
基金supported by the Guangdong Basic and Applied Basic Research Foundation(2021B1515120072)the Natural Science Foundation of China(22279096 and T2241003)the Fundamental Research Funds for the Central Universities(WUT:2023IVA094).
文摘Water electrolysis poses a significant challenge for balancing catalytic activity and stability of oxygen evolution reaction(OER)electrocatalysts.In this study,we address this challenge by constructing asymmetric redox chemistry through elaborate surface OO–Ru–OH and bulk Ru–O–Ni/Fe coordination moieties within single-atom Ru-decorated defective NiFe LDH nanosheets(Ru@d-NiFe LDH)in conjunction with strong metal-support interactions(SMSI).Rigorous spectroscopic characterization and theoretical calculations indicate that single-atom Ru can delocalize the O 2p electrons on the surface and optimize d-electron configurations of metal atoms in bulk through SMSI.The^(18)O isotope labeling experiment based on operando differential electrochemical mass spectrometry(DEMS),chemical probe experiments,and theoretical calculations confirm the encouraged surface lattice oxygen,stabilized bulk lattice oxygen,and enhanced adsorption of oxygen-containing intermediates for bulk metals in Ru@d-NiFe LDH,leading to asymmetric redox chemistry for OER.The Ru@d-NiFe LDH electrocatalyst exhibits exceptional performance with an overpotential of 230 mV to achieve 10 mA cm^(−2)and maintains high robustness under industrial current density.This approach for achieving asymmetric redox chemistry through SMSI presents a new avenue for developing high-performance electrocatalysts and instills confidence in its industrial applicability.
基金support of National Key R&D Program of China(No.2025YFE0111200)the Fundamental Research Funds for the Central Universities(No.40120631)+4 种基金the National Natural Science Foundation of China(No.52202291)Empowering Graduate Students as Scholarly Writers:Multidisciplinary Collaboration and Digital Innovation in Academic Publishing(No.zx2024006)for the supportsupport of 2025 Provincial Key R&D Program Joint Project on Science and Technology Innovation in Sanya Yazhou Bay Science and Technology City sponsored by Science and Technology Department of Hainan Province(No.ZDYF2025GXJS130)the Natural Science Foundation of Hainan Province of China(No.623MS068)the Innovation Studio Project of the Jing men Center for Technology Transfer at Wuhan University of Technology(No.WHUTJMZX-2024CX-06).
文摘The electrolysis of natural seawater powered by abundant offshore renewable energy is widely considered as a sustainable hydrogen production technique.However,the competitive chlorine evolution reaction severely damages the catalyst durability in the anodic seawater oxidation.Here,we demonstrate that the in situ chromate cover restructured from a preformed Crbased metal organic framework(MIL-101(Cr))stabilizes anodic seawater oxidation while maintaining high activity on an optimized NiFe-layered double hydroxide(NiFe-LDH)array catalyst.Impressively,such a cover enables an over 20-fold reduction in overpotential attenuation rate(0.11 mV·h^(-1))in comparison to the unmodified NiFe-LDH counterpart(2.38 mV·h^(-1))against a stable 185 h operation.A combination of experiment studies and theoretical calculations has unveiled that the in situ generated chromate cover weaken unfavorable Cl^(-)adsorption more notably over reactive OH−,therefore mitigating the Cl-related corrosion on the NiFe-LDH.The present study advances a stability breakthrough in the feasible implementation of direct seawater electrolysis for sustainable green hydrogen production.
基金This work was supported by the National Natural Science Foundation of China(No.22075223)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(No.2022-ZD-4).
文摘As the main limiting step of overall water splitting,oxygen evolution reaction(OER)is urgent to be enhanced by developing efficient catalysts to promote the process of electrolytic water.Based on theoretical analysis,the Ni-metal-organic framework(Ni-MOF)and NiFe-layered double hydroxide(NiFe-LDH)(NiFe-LDH/MOF)heterostructure can optimize the energy barrier of the OER process and decrease the adsorption energy of oxygen-containing intermediates,effectively accelerating the OER kinetics.Accordingly,layered NiFe-LDH/MOF heterostructures are in situ constructed through a facile two-step reaction process,with substantial oxygen defects and lattice defects that further improve the catalytic performance.As a result,only 208 and 275 mV OER overpotentials are needed for NiFe-LDH/MOF to drive the current densities of 20 and 100 mA·cm^(-2)in 1 M KOH solutions,and even maintain catalytic stability of 100 h at 20 mA·cm^(-2).When applied to seawater oxidation,only 235 and 307 mV OER overpotentials are required to achieve the current densities of 20 and 100 mA·cm^(-2),respectively,with almost no attenuation for 100 h stability test at 20 mA·cm^(-2),all better than commercial RuO_(2).This work provides the theoretical and experimental basis and a new idea for efficiently driving fresh water and seawater cracking by heterostructure and defect coupling design toward catalysts.
基金the financial support of the Fundamental Research Funds for the Central Universities(No.40120631)the National Natural Science Foundation of China(No.52202291)for the support.+1 种基金C.C.acknowledges the financial support of Natural Science Foundation of Hubei Province(No.2022CFB388)the Natural Science Foundation of Hainan Province of China(No.623MS068).
文摘Transition metal-based layered double hydroxides(LDHs)have been capable of working efficiently as catalysts in the basic oxygen evolution reaction(OER)for sustaining hydrogen production of alkaline water electrolysis.Nevertheless,exploring new LDH-based electrocatalysts featuring both remarkable activity and good stability is still in high demand,which is pivotal for comprehensive understanding and impressive improvement of the sluggish OER kinetics.Here,a series of bimetallic(Co and Mo)LDH arrays were designed and fabricated via a facile and controlled strategy by incorporating a Mo source into presynthesized Co-based metal-organic framework(MOF)arrays on carbon cloth(CC),named as ZIF-67/CC arrays.We found that tuning the Mo content resulted in gradual differences in the structural properties,surface morphology,and chemical states of the resulting catalysts,namely CoMox-LDH/CC(x representing the added weight of the Mo source).Gratifyingly,the best-performing CoMo_(0.20)-LDH/CC electrocatalyst demonstrates a low overpotential of only 226 mV and high stability at a current density of 10 mA·cm^(−2),which is superior to most LDH-based OER catalysts reported previously.Furthermore,it only required 1.611 V voltage to drive the overall water splitting device at the current density of 10 mA·cm^(−2).The present study represents a significant advancement in the development and applications of new OER catalysts.
基金support of the Fundamental Research Funds for the Central Universities(Grant No.40120631)National Natural Science Foundation of China(Grant No.52202291)for the support+2 种基金Dr.C.Chen acknowledges the financial support of Natural Science Foundation of Hubei Province(Grant No.2022CFB388)the Natural Science Foundation of Hainan Province of China(Grant No.623MS068)J.Wang thanks Singapore MOE for support of research conducted at the National University of Singapore(Tier 1,A-8000186-01-00).
文摘Within the framework of achieving global carbon neutrality,utilizing electrocatalytic water splitting to produce“green hydrogen”holds significant promise as an effective solution.The strategic development of economic,efficient,and robust anode oxygen evolution reaction(OER)catalysts is one of the imminent bottlenecks for scalable application of electrolyzing water into hydrogen and oxygen,particularly under actual yet harsh operating conditions such as large current density(LCD).In this review,we intend to summarize the advances and challenges in the understanding of the electrocatalytic OER at LCD.Initially,the impact of LCD on the electron transfer,mass transportation efficiency and catalyst stability is identified and summarized.Furthermore,five basic principles for catalyst design,namely the dimension of the materials,surface chemistry,creation of electron transfer pathways,synergy among nano-,micro-,and macroscale structures,and catalyst-support interaction,are systematically discussed.Specifically,the correlation between the synergistic function of the multiscale structures and the catalyst-support interaction is highlighted to direct improvements in catalyst efficiency and durability at the LCD.Finally,an outlook is prospected to further our understanding of these topics and provide related researchers with potential research areas.
