Molybdenum sulfides are promising electrocatalysts for the hydrogen evolution reaction(HER).Sand Mo‐related species have been proposed as the active site for forming adsorbed hydrogen to initiate the HER;however,the ...Molybdenum sulfides are promising electrocatalysts for the hydrogen evolution reaction(HER).Sand Mo‐related species have been proposed as the active site for forming adsorbed hydrogen to initiate the HER;however,the nature of the interaction between Mo centers and S ligands is unclear.Further,the development of cost‐effective water‐splitting systems using neutral water as a proton source for H2evolution is highly desirable,whereas the mechanism of the HER at neutral pH is rarely discussed.Here,the structural change in the Mo?Mo and S?S species in a synthesized molybdenum sulfide was monitored at neutral pH using in situ electrochemical Raman spectroscopy.Analysis of the potential dependent Raman spectra revealed that the band assigned to a terminal S?S species emerged along with synchronized changes in the frequency of the Mo?Mo,Mo3?μ3S,and Mo?S vibrational bands.This indicates that Mo?Mo bonds and terminal S?S ligands play synergistic roles in facilitating hydrogen evolution,likely via the internal reorganization of trinuclear Mo3?thio species.The nature and role of metal‐ligand interactions in the HER revealed in this study demonstrated a mechanism that is distinct from those reported previously in which the S or Mo sites function independently.展开更多
Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides...Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides have attracted attention as promising nature-inspired materials due to multiple adsorption sites which are enhanced by the covalent character of sulfur.This article summarizes the current status regarding the utilization and development of metal sulfide materials as CO_(2)RR electrocatalysts.First,the research background and basic principles of electrochemical CO_(2)RR are introduced.Next,an overview of the main obstacles to developing efficient CO_(2)RR electrocatalysts is presented.The section is followed by a summary of the empirical evidence supporting the application of metal sulfides as CO_(2)RR electrocatalysts beside nature-inspired motivation.The summary of synthesis methods of various metal sulfides is also presented.Furthermore,the paper also highlights the recent works on metal sulfide as efficient CO_(2)RR including the undertaking strategy on the activity enhancement,and finally,discusses the challenges and prospect of metal sulfides-based CO_(2)RR electrocatalysts.Despite recent efforts,metal sulfides remain relatively unexplored as materials for CO_(2)RR electrocatalytic applications.Therefore,this review aims to stimulate novel ideas and research for improved catalyst designs and functionality.展开更多
文摘Molybdenum sulfides are promising electrocatalysts for the hydrogen evolution reaction(HER).Sand Mo‐related species have been proposed as the active site for forming adsorbed hydrogen to initiate the HER;however,the nature of the interaction between Mo centers and S ligands is unclear.Further,the development of cost‐effective water‐splitting systems using neutral water as a proton source for H2evolution is highly desirable,whereas the mechanism of the HER at neutral pH is rarely discussed.Here,the structural change in the Mo?Mo and S?S species in a synthesized molybdenum sulfide was monitored at neutral pH using in situ electrochemical Raman spectroscopy.Analysis of the potential dependent Raman spectra revealed that the band assigned to a terminal S?S species emerged along with synchronized changes in the frequency of the Mo?Mo,Mo3?μ3S,and Mo?S vibrational bands.This indicates that Mo?Mo bonds and terminal S?S ligands play synergistic roles in facilitating hydrogen evolution,likely via the internal reorganization of trinuclear Mo3?thio species.The nature and role of metal‐ligand interactions in the HER revealed in this study demonstrated a mechanism that is distinct from those reported previously in which the S or Mo sites function independently.
基金The present work was supported by JSPS KAKENHI(Grant number 18H05159)in Scientific Research on Innovative Areas“Innovations for Light Energy Conversion(I4 LEC)”from MEXT,Japan,and was also supported by the JST Strategic International Collaborative Research Program(SICORP),Japan(Grant number JPMJSC18H7)International Science and Technology Cooperation Program(Grant No.2017YFE0127800),China.
文摘Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides have attracted attention as promising nature-inspired materials due to multiple adsorption sites which are enhanced by the covalent character of sulfur.This article summarizes the current status regarding the utilization and development of metal sulfide materials as CO_(2)RR electrocatalysts.First,the research background and basic principles of electrochemical CO_(2)RR are introduced.Next,an overview of the main obstacles to developing efficient CO_(2)RR electrocatalysts is presented.The section is followed by a summary of the empirical evidence supporting the application of metal sulfides as CO_(2)RR electrocatalysts beside nature-inspired motivation.The summary of synthesis methods of various metal sulfides is also presented.Furthermore,the paper also highlights the recent works on metal sulfide as efficient CO_(2)RR including the undertaking strategy on the activity enhancement,and finally,discusses the challenges and prospect of metal sulfides-based CO_(2)RR electrocatalysts.Despite recent efforts,metal sulfides remain relatively unexplored as materials for CO_(2)RR electrocatalytic applications.Therefore,this review aims to stimulate novel ideas and research for improved catalyst designs and functionality.
