Electrolysis of water is widely used for hydrogen isotope separation and the development of hydrogen evolution reaction(HER)catalysts with high selectivity and activity is of key importance.Herein,we propose single at...Electrolysis of water is widely used for hydrogen isotope separation and the development of hydrogen evolution reaction(HER)catalysts with high selectivity and activity is of key importance.Herein,we propose single atom catalysts(SACs)as promising catalysts for efficient hydrogen isotope separation.Pt SACs and Pt nanoparticles(NPs)have been fabricated on nanoarray-structured nitrogen-doped graphite foil(NGF)substrate by a polyol reduction method.The as prepared Pt1/NGF electrode exhibits high activity and selectivity toward HER with a low overpotential of 0.022 V at 10 mA·cm^(-2) and a high separation factor of 6.83 for hydrogen and deuterium separation,much better than Pt NPs counterpart.Density functional theory(DFT)calculations ascribe the high activity and selectivity to the constructed Pt-N_(2)C_(2) structure.This work develops a new opportunity for the design and application of high-efficiency and stable SACs toward hydrogen isotope separation by electrolysis of water.展开更多
Top-down strategy has been generally adopted for preparation of metal single atom catalysts(SACs)due to the simplified synthetic process,metal economics,and scalability characteristics.Herein,we propose a general top-...Top-down strategy has been generally adopted for preparation of metal single atom catalysts(SACs)due to the simplified synthetic process,metal economics,and scalability characteristics.Herein,we propose a general top-down route to convert metal nanoparticles into uniformly dispersed metal single atoms in mild electrochemical environment via a facile cathodic corrosion process.Within the synthetic process,Pt nanoparticles precursors are transformed into migrating Pt single atoms(Pt1)driven by a high negative potential;and subsequently these mobile Pt atoms are trapped and stabilized by N coordination sites of N-doped carbon paper(NCP).The as-prepared Pt1/NCP electrodes exhibit a superior catalytic activity toward hydrogen evolution reaction(HER)with a low overpotential of 0.022 V at 10 mA/cm^(2)and a low Tafel slope of 28.5 mV/dec as well as a long-term durability.Notably,the proposed electrochemical atomic migration strategy shows a promising generality for fabricating other metal single atoms(e.g.,Pd,Ir,Cu),which may open a new avenue for metallic SACs preparation.展开更多
Top-down strategy has been widely applied for synthesis of metal single atom catalysts(SACs)via converting metal nanoparticles or bulk metals into atomically dispersed species.Here,we report a simple electrochemical a...Top-down strategy has been widely applied for synthesis of metal single atom catalysts(SACs)via converting metal nanoparticles or bulk metals into atomically dispersed species.Here,we report a simple electrochemical atomic migration strategy for top-down synthesis of SACs via a facile cathodic corrosion process without involving high temperature or harsh atmosphere.Atoms of metal nanoparticles on cathode are firstly disbanded under high negative voltage,and emitted into the electrolyte in the form of atomic metal anions in Zintl phase.The escaped atomically dispersed metal species are then oxidized by water molecules and captured by the defects on the pre-added nitrogen doped carbon carriers in the electrolyte.This cathodic corrosion strategy is confirmed to be suitable for scalable synthesis of kinds of metal SACs(e.g.,Pt,Pd,and Ir)on doped carbon materials.Typically,the as-prepared nitrogen doped carbon powder supported Pt SACs exhibit superior catalytic activity toward hydrogen evolution reaction(HER)with a low overpotential of 0.024 V at 10 mA·cm^(−2)and a low Tafel slope of 29.7 mV·dec^(−1)as well as a long-term durability.展开更多
基金This work was financially supported by the National Natural Science Foundation of China(No.22109146)Institute of Materials CAEP(Nos.TP03201703,TP03201802,CX2019018,and WDZC202105).
文摘Electrolysis of water is widely used for hydrogen isotope separation and the development of hydrogen evolution reaction(HER)catalysts with high selectivity and activity is of key importance.Herein,we propose single atom catalysts(SACs)as promising catalysts for efficient hydrogen isotope separation.Pt SACs and Pt nanoparticles(NPs)have been fabricated on nanoarray-structured nitrogen-doped graphite foil(NGF)substrate by a polyol reduction method.The as prepared Pt1/NGF electrode exhibits high activity and selectivity toward HER with a low overpotential of 0.022 V at 10 mA·cm^(-2) and a high separation factor of 6.83 for hydrogen and deuterium separation,much better than Pt NPs counterpart.Density functional theory(DFT)calculations ascribe the high activity and selectivity to the constructed Pt-N_(2)C_(2) structure.This work develops a new opportunity for the design and application of high-efficiency and stable SACs toward hydrogen isotope separation by electrolysis of water.
基金supported by the National Magnetic Confinement Fusion Energy R&D Program(2022YFE03170004)the National Natural Science Foundation of China(22109146)the Foundation from Institute of Materials,China Academy of Engineering Physics(TP03201703,TP03201802,JBNY0602,and CX2019018)。
基金Foundation from Institute of Materials CAEP(Nos.TP03201703,TP03201802,and CX2019018)the National Natural Science Foundation of China(Nos.51701192 and 21706246).
文摘Top-down strategy has been generally adopted for preparation of metal single atom catalysts(SACs)due to the simplified synthetic process,metal economics,and scalability characteristics.Herein,we propose a general top-down route to convert metal nanoparticles into uniformly dispersed metal single atoms in mild electrochemical environment via a facile cathodic corrosion process.Within the synthetic process,Pt nanoparticles precursors are transformed into migrating Pt single atoms(Pt1)driven by a high negative potential;and subsequently these mobile Pt atoms are trapped and stabilized by N coordination sites of N-doped carbon paper(NCP).The as-prepared Pt1/NCP electrodes exhibit a superior catalytic activity toward hydrogen evolution reaction(HER)with a low overpotential of 0.022 V at 10 mA/cm^(2)and a low Tafel slope of 28.5 mV/dec as well as a long-term durability.Notably,the proposed electrochemical atomic migration strategy shows a promising generality for fabricating other metal single atoms(e.g.,Pd,Ir,Cu),which may open a new avenue for metallic SACs preparation.
基金National MCF Energy Research and Development Program(No.2022YFE03170004)National Natural Science Foundation of China(Nos.22109146 and 22309169)Foundation from Institute of Materials CAEP(Nos.TP03201802 and JBNY0602).
文摘Top-down strategy has been widely applied for synthesis of metal single atom catalysts(SACs)via converting metal nanoparticles or bulk metals into atomically dispersed species.Here,we report a simple electrochemical atomic migration strategy for top-down synthesis of SACs via a facile cathodic corrosion process without involving high temperature or harsh atmosphere.Atoms of metal nanoparticles on cathode are firstly disbanded under high negative voltage,and emitted into the electrolyte in the form of atomic metal anions in Zintl phase.The escaped atomically dispersed metal species are then oxidized by water molecules and captured by the defects on the pre-added nitrogen doped carbon carriers in the electrolyte.This cathodic corrosion strategy is confirmed to be suitable for scalable synthesis of kinds of metal SACs(e.g.,Pt,Pd,and Ir)on doped carbon materials.Typically,the as-prepared nitrogen doped carbon powder supported Pt SACs exhibit superior catalytic activity toward hydrogen evolution reaction(HER)with a low overpotential of 0.024 V at 10 mA·cm^(−2)and a low Tafel slope of 29.7 mV·dec^(−1)as well as a long-term durability.
