As the green and sustainable development of human society highly relies on renewable energy,it has been recognized that electrocatalysis is a key technology to this end.High efficient ways of carbon-neutralization(eCO...As the green and sustainable development of human society highly relies on renewable energy,it has been recognized that electrocatalysis is a key technology to this end.High efficient ways of carbon-neutralization(eCO_(2)RR),reverse artificial nitrogen cycle(RANC),and oxygen chemistry(OER and ORR)all can be driven by electrocatalysis.Advanced theoretical study is an important means to fundamentally understanding electrocatalytic reactions.Herein,we review a few significant issues in theoretical electrocatalysis.First,electrochemical barriers and potential effects are essential for a more accurate description of reaction mechanism and activity.Meanwhile,consideration of competitive reaction path is also one of the important aspects,as novel insights and anomalous volcano trend can be obtained.Finally,a microenvironment exerted by confined space can tune the capacitance of electrochemical interface and(electro)chemical potential of proton,resulting in a possibility to improve reaction activity,which opens a new avenue for design of catalyst.展开更多
The rational design of efficient single-atomic(SA)catalysts is essential and highly desirable but impeded by the lack of sufficient acknowledge between structure and property.To this end,it is critical to clarify the ...The rational design of efficient single-atomic(SA)catalysts is essential and highly desirable but impeded by the lack of sufficient acknowledge between structure and property.To this end,it is critical to clarify the effect of the coordination structure of active metal centers on the catalytic activities for the design of such catalysts.Here,we report that different coordination structures of SA Pt catalysts can dramatically influence their activities for anti-Markovnikov hydroboration of alkenes.Compared with the other two coordination structures(Pt-N4 and Pt-O2),the SA Pt species coordinated with three O atoms(Pt-O3)display the highest turnover number value of 3288 for the hydroboration reaction to access the important alkylboronic esters.Density functional theory calculations reveal that a superior catalytic activity can be expected for alkene hydroboration over the three O coordinated Pt species due to the lowest reaction energy(ΔG)limiting step from the reaction phase diagram.展开更多
文摘As the green and sustainable development of human society highly relies on renewable energy,it has been recognized that electrocatalysis is a key technology to this end.High efficient ways of carbon-neutralization(eCO_(2)RR),reverse artificial nitrogen cycle(RANC),and oxygen chemistry(OER and ORR)all can be driven by electrocatalysis.Advanced theoretical study is an important means to fundamentally understanding electrocatalytic reactions.Herein,we review a few significant issues in theoretical electrocatalysis.First,electrochemical barriers and potential effects are essential for a more accurate description of reaction mechanism and activity.Meanwhile,consideration of competitive reaction path is also one of the important aspects,as novel insights and anomalous volcano trend can be obtained.Finally,a microenvironment exerted by confined space can tune the capacitance of electrochemical interface and(electro)chemical potential of proton,resulting in a possibility to improve reaction activity,which opens a new avenue for design of catalyst.
基金This work was supported by the National Key R&D Program of China(2018YFA0702003)the National Natural Science Foundation of China(21890383,21671117,21871159 and 21901135).
文摘The rational design of efficient single-atomic(SA)catalysts is essential and highly desirable but impeded by the lack of sufficient acknowledge between structure and property.To this end,it is critical to clarify the effect of the coordination structure of active metal centers on the catalytic activities for the design of such catalysts.Here,we report that different coordination structures of SA Pt catalysts can dramatically influence their activities for anti-Markovnikov hydroboration of alkenes.Compared with the other two coordination structures(Pt-N4 and Pt-O2),the SA Pt species coordinated with three O atoms(Pt-O3)display the highest turnover number value of 3288 for the hydroboration reaction to access the important alkylboronic esters.Density functional theory calculations reveal that a superior catalytic activity can be expected for alkene hydroboration over the three O coordinated Pt species due to the lowest reaction energy(ΔG)limiting step from the reaction phase diagram.
