Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of ph...Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.展开更多
Water oxidation is significant in both natural and artificial photosynthesis.In nature,water oxidation occurs at the oxygen‐evolving center of photosystem II,and leads to the generation of oxygen,protons,and electron...Water oxidation is significant in both natural and artificial photosynthesis.In nature,water oxidation occurs at the oxygen‐evolving center of photosystem II,and leads to the generation of oxygen,protons,and electrons.The last two are used for fixation of carbon dioxide to give carbohydrates.In artificial processes,the coupling of water oxidation to evolve O2and water reduction to evolve H2is known as water splitting,which is an attractive method for solar energy conversion and storage.Because water oxidation is a thermodynamically uphill reaction and is kinetically slow,this reaction causes a bottleneck in large‐scale water splitting.As a consequence,the development of new and efficient water oxidation catalysts(WOCs)has attracted extensive attention.Recent efforts have identified a variety of mononuclear earth‐abundant transition‐metal complexes as active and stable molecular WOCs.This review article summarizes recent progress in research on mononuclear catalysts that are based on first‐row transition‐metal elements,namely manganese,iron,cobalt,nickel,and copper.Particular attention is paid to catalytic mechanisms and the key O?O bond formation steps.This information is critical for designing new catalysts that are highly efficient and stable.展开更多
This vertically self‐pillared(VSP)structure extends the application range of traditional porous materials with facile mass/ion transport and enhanced reaction kinetics.Here,we prepare a single crystal metal‐organic ...This vertically self‐pillared(VSP)structure extends the application range of traditional porous materials with facile mass/ion transport and enhanced reaction kinetics.Here,we prepare a single crystal metal‐organic framework(MOF),employing the ZIF‐67 structure as a proof of concept,which is constructed by vertically self‐pillared nanosheets(VSP‐MOF).We further converted VSP‐MOF into VSP‐cobalt sulfide(VSP‐CoS2)through a sulfidation process.Catalysis plays an important role in almost all battery technologies;for metallic batteries,lithium anodes exhibit a high theoretical specific capacity,low density,and low redox potential.However,during the half‐cell reaction(Li++e=Li),uncontrolled dendritic Li penetrates the separator and solid electrolyte interphase layer.When employed as a composite scaffold for lithium metal deposition,there are many advantage to using this framework:1)the VSP‐CoS2 substrate provides a high specific surface area to dissipate the ion flux and mass transfer and acts as a pre‐catalyst,2)the catalytic Co center favors the charge transfer process and preferentially binds the Li+with the enhanced electrical fields,and 3)the VSP structure guides the metallic propagation along the nanosheet 2D orientation without the protrusive dendrites.All these features enable the VSP structure in metallic batteries with encouraging performances.展开更多
文摘Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.
基金supported by Thousand Talents Program of Chinathe National Natural Science Foundation of China (21101170,21573139,and 21773146)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Research Funds of Shaanxi Normal University
文摘Water oxidation is significant in both natural and artificial photosynthesis.In nature,water oxidation occurs at the oxygen‐evolving center of photosystem II,and leads to the generation of oxygen,protons,and electrons.The last two are used for fixation of carbon dioxide to give carbohydrates.In artificial processes,the coupling of water oxidation to evolve O2and water reduction to evolve H2is known as water splitting,which is an attractive method for solar energy conversion and storage.Because water oxidation is a thermodynamically uphill reaction and is kinetically slow,this reaction causes a bottleneck in large‐scale water splitting.As a consequence,the development of new and efficient water oxidation catalysts(WOCs)has attracted extensive attention.Recent efforts have identified a variety of mononuclear earth‐abundant transition‐metal complexes as active and stable molecular WOCs.This review article summarizes recent progress in research on mononuclear catalysts that are based on first‐row transition‐metal elements,namely manganese,iron,cobalt,nickel,and copper.Particular attention is paid to catalytic mechanisms and the key O?O bond formation steps.This information is critical for designing new catalysts that are highly efficient and stable.
文摘This vertically self‐pillared(VSP)structure extends the application range of traditional porous materials with facile mass/ion transport and enhanced reaction kinetics.Here,we prepare a single crystal metal‐organic framework(MOF),employing the ZIF‐67 structure as a proof of concept,which is constructed by vertically self‐pillared nanosheets(VSP‐MOF).We further converted VSP‐MOF into VSP‐cobalt sulfide(VSP‐CoS2)through a sulfidation process.Catalysis plays an important role in almost all battery technologies;for metallic batteries,lithium anodes exhibit a high theoretical specific capacity,low density,and low redox potential.However,during the half‐cell reaction(Li++e=Li),uncontrolled dendritic Li penetrates the separator and solid electrolyte interphase layer.When employed as a composite scaffold for lithium metal deposition,there are many advantage to using this framework:1)the VSP‐CoS2 substrate provides a high specific surface area to dissipate the ion flux and mass transfer and acts as a pre‐catalyst,2)the catalytic Co center favors the charge transfer process and preferentially binds the Li+with the enhanced electrical fields,and 3)the VSP structure guides the metallic propagation along the nanosheet 2D orientation without the protrusive dendrites.All these features enable the VSP structure in metallic batteries with encouraging performances.
