The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It i...The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C6H6,HC≡C—C≡N,C6H5C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.展开更多
Boosting the alkaline hydrogen evolution and oxidation reaction(HER/HOR)kinetics is vital to practicing the renewable hydrogen cycle in alkaline media.Recently,intensive research has demonstrated that interface engine...Boosting the alkaline hydrogen evolution and oxidation reaction(HER/HOR)kinetics is vital to practicing the renewable hydrogen cycle in alkaline media.Recently,intensive research has demonstrated that interface engineering is of critical significance for improving the performance of heterostructured electrocatalysts particularly toward the electrochemical reactions involving multiple reaction intermediates like alkaline hydrogen electrocatalysis,and the research advances also bring substantial non-trivial fundamental insights accordingly.Herein,we review the current status of interface engineering with respect to developing efficient heterostructured electrocatalysts for alkaline HER and HOR.Two major subjects—how interface engineering promotes the reaction kinetics and what fundamental insights interface engineering has brought into alkaline HER and HOR—are discussed.Specifically,heterostructured electrocatalysts with abundant interfaces have shown substantially accelerated alkaline hydrogen electrocatalysis kinetics owing to the synergistic effect from different components,which could balance the adsorption/desorption behaviors of the intermediates at the interfaces.Meanwhile,interface engineering can effectively tune the electronic structures of the active sites via electronic interaction,interfacial bonding,and lattice strain,which would appropriately optimize the binding energy of targeted intermediates like hydrogen.Furthermore,the confinement effect is critical for delivering high durability by sustaining high density of active sites.At last,our own perspectives on the challenges and opportunities toward developing efficient heterostructured electrocatalysts for alkaline hydrogen electrocatalysis are provided.展开更多
基金Supported by the National Basic Research Program of China （2005CB221203）, the National Natural Science Foundation of China （20576087, 20776093） and the Foundation of Shanxi Province （2006011022, 2009021015）.
文摘The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C6H6,HC≡C—C≡N,C6H5C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.
基金funding support from “Hundred Talents Program” of Zhejiang University, Chinapartially supported by the Australian Research Council (ARC) Discovery Project (DP200100365)
文摘Boosting the alkaline hydrogen evolution and oxidation reaction(HER/HOR)kinetics is vital to practicing the renewable hydrogen cycle in alkaline media.Recently,intensive research has demonstrated that interface engineering is of critical significance for improving the performance of heterostructured electrocatalysts particularly toward the electrochemical reactions involving multiple reaction intermediates like alkaline hydrogen electrocatalysis,and the research advances also bring substantial non-trivial fundamental insights accordingly.Herein,we review the current status of interface engineering with respect to developing efficient heterostructured electrocatalysts for alkaline HER and HOR.Two major subjects—how interface engineering promotes the reaction kinetics and what fundamental insights interface engineering has brought into alkaline HER and HOR—are discussed.Specifically,heterostructured electrocatalysts with abundant interfaces have shown substantially accelerated alkaline hydrogen electrocatalysis kinetics owing to the synergistic effect from different components,which could balance the adsorption/desorption behaviors of the intermediates at the interfaces.Meanwhile,interface engineering can effectively tune the electronic structures of the active sites via electronic interaction,interfacial bonding,and lattice strain,which would appropriately optimize the binding energy of targeted intermediates like hydrogen.Furthermore,the confinement effect is critical for delivering high durability by sustaining high density of active sites.At last,our own perspectives on the challenges and opportunities toward developing efficient heterostructured electrocatalysts for alkaline hydrogen electrocatalysis are provided.
