Metal doping for active sites exhibits remarkable potential for improving the hydrogen evolution reaction(HER).Multi-doping and the use of a conductive substrate can further modulate catalytic performance.Herein,Nb-Co...Metal doping for active sites exhibits remarkable potential for improving the hydrogen evolution reaction(HER).Multi-doping and the use of a conductive substrate can further modulate catalytic performance.Herein,Nb-CoSe well dispersed in N-doped carbon nanospheres(NCs,Nb-CoSe@NC)was synthesized to serve as a conductive substrate and facilitated good dispersion of active sites for the HER.Nb doping can also change the electronic structure of CoSe,which facilitates the activity for the HER.In order to further improve the conductivity and intrinsic activity of Nb-CoSe@NC,dual,nonmetal doping was realized through gas sulfurization to prepare hierarchical Nb-CoSeS@NC.The prepared Nb-CoSeS@NC,with a core-shell structure,exhibited a low overpotential of 115 mV at 10 mA cm–2,which is smaller than that of the most doped catalysts.In addition,NCs not only improved the dispersion and conductivity of the catalyst but also prevented metal corrosion in an electrolyte,thus facilitating the long-term stability of Nb-CoSeS@NC.Moreover,the synergistic effect of the multi-doping of Nb,S,and Se was explained.This work provides a promising,multi-doping strategy for the large-scale application of transition-metal-based electrocatalysts for the HER.展开更多
The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction(HER) in alkaline media. However, it remains a challenge to...The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction(HER) in alkaline media. However, it remains a challenge to controllably create the high-density interface of double sites for optimal synergistic effect.Herein, we reported a simple chemical oxidation-induced surface reconfiguration strategy to obtain the interface-rich Fe_(3)O_(4)-FeS nanoarray supported on iron foam(Fe_(3)O_(4)-FeS/IF) using FeS nanosheets as precursors. The abundant Fe_(3)O_(4)-FeS interfaces could improve the dispersion of active sites and facilitate the electron transfer, leading to enhanced hydrogen evolution efficiency. And meanwhile, by altering the oxidation temperature, the content of S and O could be effectively controlled, further achieving the ratio optimization of Fe_(3)O_(4)to FeS. Synchrotron-based X-ray absorption near-edge structure, X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy consistently confirm the changes of electronic structure and d-band center of Fe_(3)O_(4)-FeS after chemical oxidation. Consequently, Fe_(3)O_(4)-FeS/IF exhibits excellent alkaline HER activity with a low overpotential of 120.8 mV to reach 20 mA cm^(-2),and remains stable ranging from 10, 20 to 50 mA cm^(-2) for each 20 h, respectively. Therefore, the facile and controllable chemical oxidation may be an effective strategy for designing high-density interfaces of transition metal-based sulfides towards alkaline HER.展开更多
文摘Metal doping for active sites exhibits remarkable potential for improving the hydrogen evolution reaction(HER).Multi-doping and the use of a conductive substrate can further modulate catalytic performance.Herein,Nb-CoSe well dispersed in N-doped carbon nanospheres(NCs,Nb-CoSe@NC)was synthesized to serve as a conductive substrate and facilitated good dispersion of active sites for the HER.Nb doping can also change the electronic structure of CoSe,which facilitates the activity for the HER.In order to further improve the conductivity and intrinsic activity of Nb-CoSe@NC,dual,nonmetal doping was realized through gas sulfurization to prepare hierarchical Nb-CoSeS@NC.The prepared Nb-CoSeS@NC,with a core-shell structure,exhibited a low overpotential of 115 mV at 10 mA cm–2,which is smaller than that of the most doped catalysts.In addition,NCs not only improved the dispersion and conductivity of the catalyst but also prevented metal corrosion in an electrolyte,thus facilitating the long-term stability of Nb-CoSeS@NC.Moreover,the synergistic effect of the multi-doping of Nb,S,and Se was explained.This work provides a promising,multi-doping strategy for the large-scale application of transition-metal-based electrocatalysts for the HER.
基金financially supported by National Natural Science Foundation of China (52174283)the Qingdao Science and Technology Benefiting People Special Project (20-3-4-8-nsh)+1 种基金the Fundamental Research Funds for the Central Universities(20CX02212A)the Development Fund of State Key Laboratory of Heavy Oil Processing and the Postgraduate Innovation Project of China University of Petroleum (YCX2020042)。
文摘The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction(HER) in alkaline media. However, it remains a challenge to controllably create the high-density interface of double sites for optimal synergistic effect.Herein, we reported a simple chemical oxidation-induced surface reconfiguration strategy to obtain the interface-rich Fe_(3)O_(4)-FeS nanoarray supported on iron foam(Fe_(3)O_(4)-FeS/IF) using FeS nanosheets as precursors. The abundant Fe_(3)O_(4)-FeS interfaces could improve the dispersion of active sites and facilitate the electron transfer, leading to enhanced hydrogen evolution efficiency. And meanwhile, by altering the oxidation temperature, the content of S and O could be effectively controlled, further achieving the ratio optimization of Fe_(3)O_(4)to FeS. Synchrotron-based X-ray absorption near-edge structure, X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy consistently confirm the changes of electronic structure and d-band center of Fe_(3)O_(4)-FeS after chemical oxidation. Consequently, Fe_(3)O_(4)-FeS/IF exhibits excellent alkaline HER activity with a low overpotential of 120.8 mV to reach 20 mA cm^(-2),and remains stable ranging from 10, 20 to 50 mA cm^(-2) for each 20 h, respectively. Therefore, the facile and controllable chemical oxidation may be an effective strategy for designing high-density interfaces of transition metal-based sulfides towards alkaline HER.
