Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination...Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination interface by constructing a fast electron transfer channel between Cu_(2)V_(2)O_(7)(CVO)and BiVO4(BVO).X-ray absorption spectroscopy(XAS)and theoretical calculations results confirm that CVO and BVO between interfaces are bonded by the way of unsaturated coordination oxygen(Ouc).The Ouc optimizes the O-O coupled energy barrier at the V active site and promotes the disconnection of O-H bond,which increases the photocurrent intensity of CVO by 6 times.In addition,due to the high electronegativity of the Ouc,the bonding energies of Bi-O and Cu-O at the interface are enhanced,resulting in the long-term stability of the photoanode during the water splitting.Finally,by integrating the working electrode with a polysilicon solar cell,we assembled a device that demonstrated exceptional catalytic performance,achieving a hydrogen production rate of 100.6μmol·cm^(-2),and maintaining a hydrogen-to-oxygen volume ratio of 2:1 after continuous operation for 4 h.This discovery aids in a deeper understanding of photoanode design and offers further insights for industrial applications.展开更多
We report in situ doping of brushite on zinc manganese oxide（ZMO）, fabricated by calcining a Mn（II） oxalate‐impregnated metal‐organic framework. The doping process was conducted in com‐bination with the photoca...We report in situ doping of brushite on zinc manganese oxide（ZMO）, fabricated by calcining a Mn（II） oxalate‐impregnated metal‐organic framework. The doping process was conducted in com‐bination with the photocatalytic water oxidation reaction which was catalyzed by ZMO in neutral phosphate‐buffered aqueous solution containing [Ru（bpy）3]^2＋‐Na2S2O8 and calcium（II） triflate salt, exhibiting greatly enhanced water oxidation performance with optimized turnover frequency of 0.18 mmol（O2） mol（Mn）^（–1） s^（–1）. Different analytical techniques indicated that photodeposited calci‐um‐phosphate（CaP） acted as a co‐catalyst to promote the O2 evolution activity of ZMO. This system involved the use of manganese oxide and calcium ion, and the operation was conducted under am‐bient temperature and neutral conditions, thus, it efficiently mimicked the oxygen‐evolving complex in photosystem II.展开更多
The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and...The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and realizing the precise manipulation of the reaction process remains challenging.Herein,through constructing a nanosheet assembled sunflower-like Co(OH)_(2) with Ir,Fe codoping,the electronic structure and binding strengths with oxygen-involved intermediates of Co active sites are considerably moderated.First-principles calculations and comprehensive characterizations suggest that Fe and Ir codoping significantly lowers the electrochemical reaction barrier and promotes the OER reaction kinetics by precisely accelerating the formation process of*O.Moreover,the nanosheet-assembled open architectures enable the catalyst with plentiful catalytically active sites and facilitate mass transport and electron transfer.As a result,the optimal electrocatalyst can exhibit outstanding oxygen-evolving activity with an ultralow overpotential of 254 mV at 10 mA cm^(-2).This study realizes the precise manipulation of the reaction energy barrier of OER via Ir,Fe dual doping,which will be a generic paradigm for designing advanced yet cost-effective electrocatalysts.展开更多
Direct seawater electrolysis is key to massive hydrogen fuel production without the depletion of precious freshwater resources and the need for high-purity electrolytes.However,the presence of high-concentration chlor...Direct seawater electrolysis is key to massive hydrogen fuel production without the depletion of precious freshwater resources and the need for high-purity electrolytes.However,the presence of high-concentration chloride ions(Cl^(-))and alkaline-earth metal ions(Mg^(2+),Ca^(2+))poses great challenges to the stability and selectivity of the catalysts for seawater splitting.展开更多
The development of highly efficient and inexpensive catalysts for oxygen evolving reactions （OERs） is extremely urgent for promoting the overall efficiency of water splitting. Herein we report the fabrication of a s...The development of highly efficient and inexpensive catalysts for oxygen evolving reactions （OERs） is extremely urgent for promoting the overall efficiency of water splitting. Herein we report the fabrication of a series of amorphous NiFeB nanoparticles with varying atomic ratios of Fe to （Ni ＋ Fe） （XFe） by a facile chemical-reduction method. The amorphous NiFeB （XFe=0.20） nanoparticles, combining the merits of in situ formation of borate-enriched NiFeOOH catalytic surface layers, intrinsic amorphous nanostructures, and an optimized degree of Fe doping, displayed highly active electrocatalytic performance towards the OER in a broad range of pH values （from alkaline to neutral conditions）. The catalyst exhibited a relatively low overpotential of 216 mV with a Tafel slope of 40 mWdec on Ni foam and 251 mV with a Tafel slope of 43 mV/dec on glassy carbon at 10 mA/cm2 in a 1 M KOH solution, demonstrating much greater OER efficiency than that of commercial RuO2. Long-term stability testing of the OER performance of NiFeB （XFe = 0.20） by chronoamperometry （overpotential （η） = 320 mV） over 200 h revealed no evidence of degradation. Facile, scalable synthesis and highly active water oxidation make the NiFeB nanoparticles very attractive for OER electrocatalysis.展开更多
The design and fabrication of low-cost, high-effidency, and stable oxygen-evolving catalysts are essential for promoting the overall efficiency of water electrolysis. In this study, mesoporous Ni1-xFexOy （0 〈 x 〈 1...The design and fabrication of low-cost, high-effidency, and stable oxygen-evolving catalysts are essential for promoting the overall efficiency of water electrolysis. In this study, mesoporous Ni1-xFexOy （0 〈 x 〈 1, 1 〈y 〈 1.5） nanorods were synthesized by the facile thermal decomposition of Ni-Fe-based coordination polymers. These polymers passed their nanorod-like morphology to oxides, which served as active catalysts for oxygen evolution reaction （OER）. Increasing the Fe-doping amount to 33 at.% decreased the particle size and charge-transfer resistance and increased the surface area, resulting in a reduced overpotential （-302 mV） at 10 mA/cm^2 and a reduced Tafel slope （-42 mV/dec）, which were accompanied by a far improved OER activity compared with those of commercial RuO2 and IrO2 electrocatalysts. At Fe-doping concentrations higher than 33 at.%, the trend of the electrocatalytic parameters started to reverse. The shift in the dopant concentration of Fe was further reflected in the structural transformation from a NiO （〈33 at.% Fe） rock-salt structure to a biphasic NiO/NiFe204 （33 at.% Fe） heterostructure, a NiFe204 （66 at.% Fe） spinel structure, and eventually to α-fe203 （100 at.% Fe）. The efficient water-oxidation activity is ascribed to the highly mesoporous one-dimensional nanostructure, large surface area, and optimal amounts of the dopant Fe. The merits of abundance in the Earth, scalable synthesis, and highly efficient electrocatalytic activity make mesoporous Ni-Fe binary oxides promising oxygen-evolving catalysts for water splitting.展开更多
Heat denaturation is an important technique in the study of the structure and function of photosynthetic proteins. Heat denaturation of photosystem II (PSII) membrane was studied using circular dichroism (CD) spect...Heat denaturation is an important technique in the study of the structure and function of photosynthetic proteins. Heat denaturation of photosystem II (PSII) membrane was studied using circular dichroism (CD) spectroscopy, differential scanning calorimetry (DSC) and oxygen electrode. Complete loss of oxygen evolving activity of the PSII membrane was observed at temperatures below 45℃ . The decrease of excitonic interaction between chlorophyll molecules occurred more rapidly than the change of the protein secondary structure of the PSII membrane at temperatures above 45℃ . The results indicate that the protein secondary structure of the membrane proteins in PSII membranes is more stable than the excitonic interaction between chlorophyll molecules during heat denaturation.展开更多
基金supported by the Natural Science Foundation of China(Nos.22278094 and 22379033)Guangdong Graduate Education Innovation Program(No.2023JGXM_102)+2 种基金the Basic and Applied Basic Research Program of Guangzhou(No.SL2024A03J00499)the University Innovation Team Scientific Research Project of Guangzhou(No.202235246)Hainan Province Graduate Innovation Research Project(No.Qhyb2023-143).
文摘Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination interface by constructing a fast electron transfer channel between Cu_(2)V_(2)O_(7)(CVO)and BiVO4(BVO).X-ray absorption spectroscopy(XAS)and theoretical calculations results confirm that CVO and BVO between interfaces are bonded by the way of unsaturated coordination oxygen(Ouc).The Ouc optimizes the O-O coupled energy barrier at the V active site and promotes the disconnection of O-H bond,which increases the photocurrent intensity of CVO by 6 times.In addition,due to the high electronegativity of the Ouc,the bonding energies of Bi-O and Cu-O at the interface are enhanced,resulting in the long-term stability of the photoanode during the water splitting.Finally,by integrating the working electrode with a polysilicon solar cell,we assembled a device that demonstrated exceptional catalytic performance,achieving a hydrogen production rate of 100.6μmol·cm^(-2),and maintaining a hydrogen-to-oxygen volume ratio of 2:1 after continuous operation for 4 h.This discovery aids in a deeper understanding of photoanode design and offers further insights for industrial applications.
文摘We report in situ doping of brushite on zinc manganese oxide（ZMO）, fabricated by calcining a Mn（II） oxalate‐impregnated metal‐organic framework. The doping process was conducted in com‐bination with the photocatalytic water oxidation reaction which was catalyzed by ZMO in neutral phosphate‐buffered aqueous solution containing [Ru（bpy）3]^2＋‐Na2S2O8 and calcium（II） triflate salt, exhibiting greatly enhanced water oxidation performance with optimized turnover frequency of 0.18 mmol（O2） mol（Mn）^（–1） s^（–1）. Different analytical techniques indicated that photodeposited calci‐um‐phosphate（CaP） acted as a co‐catalyst to promote the O2 evolution activity of ZMO. This system involved the use of manganese oxide and calcium ion, and the operation was conducted under am‐bient temperature and neutral conditions, thus, it efficiently mimicked the oxygen‐evolving complex in photosystem II.
基金supported by the start-up funding to H.Xu from Changzhou University(ZMF22020055)grants from Advanced Catalysis and Green Manufacturing Collaborative Innovation Center(ACGM2022-10-01),Changzhou University.
文摘The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and realizing the precise manipulation of the reaction process remains challenging.Herein,through constructing a nanosheet assembled sunflower-like Co(OH)_(2) with Ir,Fe codoping,the electronic structure and binding strengths with oxygen-involved intermediates of Co active sites are considerably moderated.First-principles calculations and comprehensive characterizations suggest that Fe and Ir codoping significantly lowers the electrochemical reaction barrier and promotes the OER reaction kinetics by precisely accelerating the formation process of*O.Moreover,the nanosheet-assembled open architectures enable the catalyst with plentiful catalytically active sites and facilitate mass transport and electron transfer.As a result,the optimal electrocatalyst can exhibit outstanding oxygen-evolving activity with an ultralow overpotential of 254 mV at 10 mA cm^(-2).This study realizes the precise manipulation of the reaction energy barrier of OER via Ir,Fe dual doping,which will be a generic paradigm for designing advanced yet cost-effective electrocatalysts.
基金supported by the National Natural Science Foundation of China(21872019,22279013)l Chengdu Municipal Science and Technology Bureau(2022-YF05-00783-SN)lsupported by the Slovenian Research Agency under Grants No.P2-0412 and J2-2498 for Andraz Mavric and Matjaz Valant and Z1-3189 for Nadiia Pastukhova.
文摘Direct seawater electrolysis is key to massive hydrogen fuel production without the depletion of precious freshwater resources and the need for high-purity electrolytes.However,the presence of high-concentration chloride ions(Cl^(-))and alkaline-earth metal ions(Mg^(2+),Ca^(2+))poses great challenges to the stability and selectivity of the catalysts for seawater splitting.
基金We appreciate the financial funding supported by the National Natural Science Foundation of China （No. 51402205）, Natural Science Foundation of Shanxi （No. 2015021058） and Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi （No. STIP-2016131）.
文摘The development of highly efficient and inexpensive catalysts for oxygen evolving reactions （OERs） is extremely urgent for promoting the overall efficiency of water splitting. Herein we report the fabrication of a series of amorphous NiFeB nanoparticles with varying atomic ratios of Fe to （Ni ＋ Fe） （XFe） by a facile chemical-reduction method. The amorphous NiFeB （XFe=0.20） nanoparticles, combining the merits of in situ formation of borate-enriched NiFeOOH catalytic surface layers, intrinsic amorphous nanostructures, and an optimized degree of Fe doping, displayed highly active electrocatalytic performance towards the OER in a broad range of pH values （from alkaline to neutral conditions）. The catalyst exhibited a relatively low overpotential of 216 mV with a Tafel slope of 40 mWdec on Ni foam and 251 mV with a Tafel slope of 43 mV/dec on glassy carbon at 10 mA/cm2 in a 1 M KOH solution, demonstrating much greater OER efficiency than that of commercial RuO2. Long-term stability testing of the OER performance of NiFeB （XFe = 0.20） by chronoamperometry （overpotential （η） = 320 mV） over 200 h revealed no evidence of degradation. Facile, scalable synthesis and highly active water oxidation make the NiFeB nanoparticles very attractive for OER electrocatalysis.
文摘The design and fabrication of low-cost, high-effidency, and stable oxygen-evolving catalysts are essential for promoting the overall efficiency of water electrolysis. In this study, mesoporous Ni1-xFexOy （0 〈 x 〈 1, 1 〈y 〈 1.5） nanorods were synthesized by the facile thermal decomposition of Ni-Fe-based coordination polymers. These polymers passed their nanorod-like morphology to oxides, which served as active catalysts for oxygen evolution reaction （OER）. Increasing the Fe-doping amount to 33 at.% decreased the particle size and charge-transfer resistance and increased the surface area, resulting in a reduced overpotential （-302 mV） at 10 mA/cm^2 and a reduced Tafel slope （-42 mV/dec）, which were accompanied by a far improved OER activity compared with those of commercial RuO2 and IrO2 electrocatalysts. At Fe-doping concentrations higher than 33 at.%, the trend of the electrocatalytic parameters started to reverse. The shift in the dopant concentration of Fe was further reflected in the structural transformation from a NiO （〈33 at.% Fe） rock-salt structure to a biphasic NiO/NiFe204 （33 at.% Fe） heterostructure, a NiFe204 （66 at.% Fe） spinel structure, and eventually to α-fe203 （100 at.% Fe）. The efficient water-oxidation activity is ascribed to the highly mesoporous one-dimensional nanostructure, large surface area, and optimal amounts of the dopant Fe. The merits of abundance in the Earth, scalable synthesis, and highly efficient electrocatalytic activity make mesoporous Ni-Fe binary oxides promising oxygen-evolving catalysts for water splitting.
基金Supported by the State Key Basic Research and Development Plan (No.G19980 10 10 0 ) the National Natural Science Foundation of China(No.3 9890 3 90 )
文摘Heat denaturation is an important technique in the study of the structure and function of photosynthetic proteins. Heat denaturation of photosystem II (PSII) membrane was studied using circular dichroism (CD) spectroscopy, differential scanning calorimetry (DSC) and oxygen electrode. Complete loss of oxygen evolving activity of the PSII membrane was observed at temperatures below 45℃ . The decrease of excitonic interaction between chlorophyll molecules occurred more rapidly than the change of the protein secondary structure of the PSII membrane at temperatures above 45℃ . The results indicate that the protein secondary structure of the membrane proteins in PSII membranes is more stable than the excitonic interaction between chlorophyll molecules during heat denaturation.
