The intrinsic activity of Co(OH)_(2) for oxygen evolution reaction(OER)may be elaborately improved through the suitable valence adjustment.Ce modification at electronic level is proved to be an efficient strategy owin...The intrinsic activity of Co(OH)_(2) for oxygen evolution reaction(OER)may be elaborately improved through the suitable valence adjustment.Ce modification at electronic level is proved to be an efficient strategy owing to the flexible transformation of Ce^(3+)/Ce4+.Herein,Ce0.21@Co(OH)_(2) with the optimized Ce doping have been fabricated to tailor the fast electron transfer for the enhanced activity and stability for OER.Firstly,the obtained core-shell structure composed of vertical loose Co(OH)_(2) sheets not only exposes a large number of active sites,but also provides channels for Ce doping.Secondly,the high pressure microwave with instantaneous heating can fast introduce Ce into Co(OH)_(2),obtaining Cex@Co(OH)_(2) with well dispersion and close integration.The intimated interaction between Ce and Co species may provide the"d-f electronic ladders"for accelerating electron transfer of the catalytic surface.Meanwhile,Ce promotes the formation of Co-superoxide intermediate and/or the release of oxygen,which is considered to be the rate-determining step for OER.The electrochemical measurements confirmed the low overpotential of 300 m V at 10 m A cm^(-2) and great stability of Ce0.21@Co(OH)_(2) for OER.This work demonstrates a meaningful approach to realize the tuned electronic structure through metal doping.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
基金financially supported by the National Natural Science Foundation of China(21776314)the Qingdao Science and Technology Benefiting People Special Project(20-3-4-8-nsh)+2 种基金the Fundamental Research Funds for the Central Universities(20CX02212A)the Development Fund of State Key Laboratory of Heavy Oil Processingthe Postgraduate Innovation Project of China University of Petroleum(YCX2020046)。
文摘The intrinsic activity of Co(OH)_(2) for oxygen evolution reaction(OER)may be elaborately improved through the suitable valence adjustment.Ce modification at electronic level is proved to be an efficient strategy owing to the flexible transformation of Ce^(3+)/Ce4+.Herein,Ce0.21@Co(OH)_(2) with the optimized Ce doping have been fabricated to tailor the fast electron transfer for the enhanced activity and stability for OER.Firstly,the obtained core-shell structure composed of vertical loose Co(OH)_(2) sheets not only exposes a large number of active sites,but also provides channels for Ce doping.Secondly,the high pressure microwave with instantaneous heating can fast introduce Ce into Co(OH)_(2),obtaining Cex@Co(OH)_(2) with well dispersion and close integration.The intimated interaction between Ce and Co species may provide the"d-f electronic ladders"for accelerating electron transfer of the catalytic surface.Meanwhile,Ce promotes the formation of Co-superoxide intermediate and/or the release of oxygen,which is considered to be the rate-determining step for OER.The electrochemical measurements confirmed the low overpotential of 300 m V at 10 m A cm^(-2) and great stability of Ce0.21@Co(OH)_(2) for OER.This work demonstrates a meaningful approach to realize the tuned electronic structure through metal doping.
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.