The design of non-noble metal heterogeneous catalyst with superior performance for selective hydrogenation or transfer hydrogenation of nitroarenes to amines is significant but challenging.Herein,a single-atom Fe supp...The design of non-noble metal heterogeneous catalyst with superior performance for selective hydrogenation or transfer hydrogenation of nitroarenes to amines is significant but challenging.Herein,a single-atom Fe supported by nitrogen-doped carbon(Fe_(1)/N-C)catalyst is reported.The Fe_(1)/N-C sample shows superior performances for the selective hydrogenation and transfer hydrogenation of nitrobenzene to aniline at different temperatures.Density functional theory(DFT)calculations show that the superior catalytic activity for the selective hydrogenation at lower temperatures could be attributed to the effective activation of the reactant and intermediates by the Fe_(1)/N-C.Moreover,the excellent performance of Fe_(1)/N-C for the selective transfer hydrogenation could be attributed to that the reaction energy barrier for dehydrogenation of isopropanol can be overcome by elevated temperatures.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
Portable electrochemical synthesis of H_(2)O_(2),which is widely used for disinfection,sterilization,and waste treatment,has attracted increasing attention.However,low atomic utilization efficiency and by-product disp...Portable electrochemical synthesis of H_(2)O_(2),which is widely used for disinfection,sterilization,and waste treatment,has attracted increasing attention.However,low atomic utilization efficiency and by-product disposal during the synthesis of electrocatalysts are inevitable.Based on the advantages of single-atom catalysts(SACs)towards H_(2)O_(2)synthesis via a 2e−transfer oxygen reduction reaction,this work presents the synthesis of ZnNC SACs as excellent oxygen reduction catalysts with high atomic use efficiency and almost no generated waste by using formamide and metal powder as precursors.The ZnNC SACs exhibit H_(2)O_(2)selectivity exceeding 80%when working continuously for 10,000 s.The synthetic strategy described in this paper is intended to be used as a supplement to the synthesis of metal-nitrogen-carbon SACs with high atomic utilization efficiency and low waste generation for environmental and chemical applications.展开更多
基金the National Key R&D Program of China(2018YFA0702003)the National Natural Science Foundation of China(21890383,21671117,21871159 and21901135)the Science and Technology Key Project of Guangdong Province of China(2020B010188002)。
文摘The design of non-noble metal heterogeneous catalyst with superior performance for selective hydrogenation or transfer hydrogenation of nitroarenes to amines is significant but challenging.Herein,a single-atom Fe supported by nitrogen-doped carbon(Fe_(1)/N-C)catalyst is reported.The Fe_(1)/N-C sample shows superior performances for the selective hydrogenation and transfer hydrogenation of nitrobenzene to aniline at different temperatures.Density functional theory(DFT)calculations show that the superior catalytic activity for the selective hydrogenation at lower temperatures could be attributed to the effective activation of the reactant and intermediates by the Fe_(1)/N-C.Moreover,the excellent performance of Fe_(1)/N-C for the selective transfer hydrogenation could be attributed to that the reaction energy barrier for dehydrogenation of isopropanol can be overcome by elevated temperatures.
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.
基金financially supported by the National Key Research and Development Program of China (2018YFA0702002)the National Natural Science Foundation of China (21935001, 22101015, 22175012 and 22005022)+3 种基金the Royal Society and Newton Fund through Newton Advanced Fellowship award (NAFR1191294)the Program for Changjiang Scholars and Innovation Research Team in the University (IRT1205)the Fundamental Research Funds for the Central Universities, Beijing Natural Science Foundation (2214062)the S&T Program of Hebei (21344601D)
文摘Portable electrochemical synthesis of H_(2)O_(2),which is widely used for disinfection,sterilization,and waste treatment,has attracted increasing attention.However,low atomic utilization efficiency and by-product disposal during the synthesis of electrocatalysts are inevitable.Based on the advantages of single-atom catalysts(SACs)towards H_(2)O_(2)synthesis via a 2e−transfer oxygen reduction reaction,this work presents the synthesis of ZnNC SACs as excellent oxygen reduction catalysts with high atomic use efficiency and almost no generated waste by using formamide and metal powder as precursors.The ZnNC SACs exhibit H_(2)O_(2)selectivity exceeding 80%when working continuously for 10,000 s.The synthetic strategy described in this paper is intended to be used as a supplement to the synthesis of metal-nitrogen-carbon SACs with high atomic utilization efficiency and low waste generation for environmental and chemical applications.