Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,in...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.展开更多
The Rashba effect plays a vital role in electronic structures and related functional properties.The strength of the Rashba effect can be measured by the Rashba parameter α_(R);it is desirable to manipulate α_(R) to ...The Rashba effect plays a vital role in electronic structures and related functional properties.The strength of the Rashba effect can be measured by the Rashba parameter α_(R);it is desirable to manipulate α_(R) to control the functional properties.The current work illustrates how α_(R) can be systematically tuned by doping,taking BiTeI as an example.展开更多
基金the National Natural Science Foundation of China(22279044,12034002,and 22202080)the Project for Self-Innovation Capability Construction of Jilin Province Development and Reform Commission(2021C026)+1 种基金Jilin Province Science and Technology Development Program(20210301009GX)the Fundamental Research Funds for the Central Universities.
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.
基金the National Natural Science Foundation of China(51872116 and 12034002)the Project for Self-Innovation Capability Construction of Jilin Province Development and Reform Commission(2021C026)+2 种基金the Program for JLU Science and Technology Innovative Research Team(JLUSTIRT-2017TD-09)the Science and Technology Development Program of Jilin Province(20190201233JC)the Fundamental Research Funds for the Central Universities.The work was carried out at LvLiang Cloud Computing Center of China,and the calculations were performed on TianHe-2.
基金This work was supported by the National Key Research and Development Program of China(Nos.2017YFB0701600,2018YFB0703600)the Natural Science Foundation of China(Grant Nos.51632005,11604200,11674211,and 51761135127)+5 种基金the 111 Project D16002W.Z.also acknowledges the support from the Guangdong Innovation Research Team Project(No.2017ZT07C062)Guangdong Provincial Key-Lab program(No.2019B030301001)Shenzhen Municipal Key-Lab program(ZDSYS20190902092905285)Shenzhen Pengcheng-Scholarship ProgramJ.Y.acknowledges the financial support of the US National Science Foundation with award number 1915933.
文摘The Rashba effect plays a vital role in electronic structures and related functional properties.The strength of the Rashba effect can be measured by the Rashba parameter α_(R);it is desirable to manipulate α_(R) to control the functional properties.The current work illustrates how α_(R) can be systematically tuned by doping,taking BiTeI as an example.
