Developing efficient,durable,and precious metal-free electrocatalysts is currently a huge challenge.In this article,through a simple one-step high-temperature pyrolysis method,by incorporating various non-metallic ele...Developing efficient,durable,and precious metal-free electrocatalysts is currently a huge challenge.In this article,through a simple one-step high-temperature pyrolysis method,by incorporating various non-metallic element atoms,we prepared four different NiX(X=Cl_(2),(CH_(3)COO)_(2),(NO_(3))2,SO_(4))@CNT catalysts.Additionally,by adjusting the temperature,these four materials were expanded into twelve catalyst materials for comparative optimization of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activity.Ultimately,Ni(NO_(3))2@CNT-900 typically exhibits superior OER and HER activity.In 1 mol/L KOH solution with a current density of 10 mA/cm^(2),the overpotentials of HER and OER of Ni(NO_(3))2@CNT-900 are only 145 mV and 300 mV,respectively.Furthermore,the Ni(NO_(3))2@CNT-900 shows excellent durability in both HER and OER.展开更多
Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as ...Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.展开更多
Using carbon felt, polytetrafluoroethylene latex and powder catalyst to assembly a light energy conversion device, the photocatalytic activity of catalyst 2.0%WO3-TiO2 （2%WO3 compounding TiO2） with oxygen vacancies ...Using carbon felt, polytetrafluoroethylene latex and powder catalyst to assembly a light energy conversion device, the photocatalytic activity of catalyst 2.0%WO3-TiO2 （2%WO3 compounding TiO2） with oxygen vacancies was studied through the water splitting for O2 evolution, using a high pressure mercury lamp as the light source and Fe^3＋ as the electron acceptor in two different devices： an ordinary photolysis device with catalyst powder suspending through a magnetic stirrer and a self-assembly light energy conversion device. The results show that after 12 h irradiation, the photocatalytic activity of 2.0%WO3-TiO2 with oxygen vacancies in the self-assembly light energy conversion device is higher than that of the ordinary photolysis device, and the amount of oxygen evolution is about 12 and 9 mmol/L respectively in these two devices. After 12 h, the rates of 02 evolution are slow in each device and the photocatalyst almost loses the photoactivity in the ordinary photolysis device. So, compared with the ordinary photocatalytic device, the rate of oxygen evolution and the life time of the catalyst are improved in the self-assembly light energy conversion device.展开更多
The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplore...The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.展开更多
Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator s...Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.展开更多
基金Project(145209113)supported by the Basic Research Expenses of Department of Education of Heilongjiang Province,China。
文摘Developing efficient,durable,and precious metal-free electrocatalysts is currently a huge challenge.In this article,through a simple one-step high-temperature pyrolysis method,by incorporating various non-metallic element atoms,we prepared four different NiX(X=Cl_(2),(CH_(3)COO)_(2),(NO_(3))2,SO_(4))@CNT catalysts.Additionally,by adjusting the temperature,these four materials were expanded into twelve catalyst materials for comparative optimization of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activity.Ultimately,Ni(NO_(3))2@CNT-900 typically exhibits superior OER and HER activity.In 1 mol/L KOH solution with a current density of 10 mA/cm^(2),the overpotentials of HER and OER of Ni(NO_(3))2@CNT-900 are only 145 mV and 300 mV,respectively.Furthermore,the Ni(NO_(3))2@CNT-900 shows excellent durability in both HER and OER.
基金the National Basic Research Development of China(2011CB936003)the National Natural Science Foundation of China(50971116)。
文摘Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.
基金Project(2010CL04) supported by the Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, ChinaProject(K-081025) supported by State Key Laboratory Breeding Base of Photocatalysis,Fuzhou University,China
文摘Using carbon felt, polytetrafluoroethylene latex and powder catalyst to assembly a light energy conversion device, the photocatalytic activity of catalyst 2.0%WO3-TiO2 （2%WO3 compounding TiO2） with oxygen vacancies was studied through the water splitting for O2 evolution, using a high pressure mercury lamp as the light source and Fe^3＋ as the electron acceptor in two different devices： an ordinary photolysis device with catalyst powder suspending through a magnetic stirrer and a self-assembly light energy conversion device. The results show that after 12 h irradiation, the photocatalytic activity of 2.0%WO3-TiO2 with oxygen vacancies in the self-assembly light energy conversion device is higher than that of the ordinary photolysis device, and the amount of oxygen evolution is about 12 and 9 mmol/L respectively in these two devices. After 12 h, the rates of 02 evolution are slow in each device and the photocatalyst almost loses the photoactivity in the ordinary photolysis device. So, compared with the ordinary photocatalytic device, the rate of oxygen evolution and the life time of the catalyst are improved in the self-assembly light energy conversion device.
基金supported by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L574)the Guizhou Provincial Science and Technology Foundation([2024]ZK General 425 and 438)+1 种基金the National Natural Science Foundation of China(22309033)the Academic Young Talent Foundation of Guizhou Normal University([2022]B05 and B06)。
文摘The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.
文摘Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.
