The electrochemical reduction of carbon dioxide(CO_(2))into value‐added fuels and chemicals presents a sustainable route to alleviate CO_(2) emissions,promote carbon‐neutral cycles and reduce the dependence on fossi...The electrochemical reduction of carbon dioxide(CO_(2))into value‐added fuels and chemicals presents a sustainable route to alleviate CO_(2) emissions,promote carbon‐neutral cycles and reduce the dependence on fossil fuels.Considering the thermodynamic stability of the CO_(2) molecule and sluggish reaction kinetics,it is still a challenge to design highly efficient electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).It has been found that the surface and interface chemistry of electrocatalysts can modulate the electronic structure and increase the active sites,which is favorable for CO_(2) adsorption,electron transfer,mass transport,and optimizing adsorption strength of reaction intermediates.However,the effect of surface and interface chemistry on metal‐free electrocatalysts(MFEs)for CO_(2)RR has not been comprehensively reviewed.Herein,we discuss the importance of the surface and interface chemistry on MFEs for improving the electrochemical CO_(2)RR performance based on thermodynamic and kinetic views.The fundamentals and challenges of CO_(2)RR are firstly presented.Then,the recent advances of the surface and interface chemistry in improving reaction rate and overcoming reaction constraints are reviewed from regulating electronic structure,active sites,electron transfer,mass transport,and intermediate binding energy.Finally,the research challenges and prospects are proposed to suggest the future designs of advanced MFEs in CO_(2)RR.展开更多
Synchrotron radiation photoemission spectroscopy was used to study the formation process of Er2O3/Si（001） imerface and film during epitaxial growth on Si. A shift in the O core-level binding energy was found accompa...Synchrotron radiation photoemission spectroscopy was used to study the formation process of Er2O3/Si（001） imerface and film during epitaxial growth on Si. A shift in the O core-level binding energy was found accompanied by a shift in the Er2O3 valence band maximum. This shift depended on the oxide layer thickness and interfacial structure. An interfacial layer was observed at the initial growth of Er2O3 film on Si, which was supposed to be attributed to the effect of Er atom catalytic oxidation effect.展开更多
基金CSIRO Energy Centre and Kick‐Start ProjectAustralian Research Council(ARC)Future Fellowships,Grant/Award Numbers:FT210100298,FT210100806+9 种基金Key Project of Scientific Research of the Education Department of Liaoning Province,Grant/Award Number:LZD201902National Natural Science Foundation of China,Grant/Award Numbers:51873085,52071171Liaoning Revitalization Talents Program‐Pan Deng Scholars,Grant/Award Numbers:XLYC1802005,XLYC2007056Industrial Transformation Training Centre,Grant/Award Number:IC180100005Shenyang Science and Technology Project,Grant/Award Number:21‐108‐9‐04veski-Study Melbourne Research Partnerships(SMRP)projectLiaoning BaiQianWan Talents Program,Grant/Award Number:LNBQW2018B0048Natural Science Fund of Liaoning Province for Excellent Young Scholars,Grant/Award Number:2019‐YQ‐04Discovery Project,Grant/Award Number:DP220100603Linkage project,Grant/Award Number:LP210100467。
文摘The electrochemical reduction of carbon dioxide(CO_(2))into value‐added fuels and chemicals presents a sustainable route to alleviate CO_(2) emissions,promote carbon‐neutral cycles and reduce the dependence on fossil fuels.Considering the thermodynamic stability of the CO_(2) molecule and sluggish reaction kinetics,it is still a challenge to design highly efficient electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).It has been found that the surface and interface chemistry of electrocatalysts can modulate the electronic structure and increase the active sites,which is favorable for CO_(2) adsorption,electron transfer,mass transport,and optimizing adsorption strength of reaction intermediates.However,the effect of surface and interface chemistry on metal‐free electrocatalysts(MFEs)for CO_(2)RR has not been comprehensively reviewed.Herein,we discuss the importance of the surface and interface chemistry on MFEs for improving the electrochemical CO_(2)RR performance based on thermodynamic and kinetic views.The fundamentals and challenges of CO_(2)RR are firstly presented.Then,the recent advances of the surface and interface chemistry in improving reaction rate and overcoming reaction constraints are reviewed from regulating electronic structure,active sites,electron transfer,mass transport,and intermediate binding energy.Finally,the research challenges and prospects are proposed to suggest the future designs of advanced MFEs in CO_(2)RR.
基金supported by the Special Project of Shanghai Nano Technology (0852nm02400 and 0752nm012)Shaoxing Science and Technology Commission (2007A21015)+3 种基金Shanghai Rising-Star Program (07QA14026)the National Natural Science Foundation of China (10804072)the Key Fundamental Project of Shanghai (08JC1410400)Shanghai Education Commission (07zz143)
文摘Synchrotron radiation photoemission spectroscopy was used to study the formation process of Er2O3/Si（001） imerface and film during epitaxial growth on Si. A shift in the O core-level binding energy was found accompanied by a shift in the Er2O3 valence band maximum. This shift depended on the oxide layer thickness and interfacial structure. An interfacial layer was observed at the initial growth of Er2O3 film on Si, which was supposed to be attributed to the effect of Er atom catalytic oxidation effect.
