配位结构主导单原子Pt的烯烃反马氏硼氢化催化性能

Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes

单原子催化剂的高效合理设计具有十分重要的意义,但是目前对于结构和性能之间的关联关系认知不足,严重阻碍了催化剂的发展进程.因此,清晰阐释金属活性中心的配位结构对于其催化性能的影响将有利于单原子催化剂的高效设计.本文研究报道了单原子Pt催化剂的活性中心配位结构显著影响其在烯烃反马氏硼氢化反应中的性能表现.三个O原子配位的Pt单原子催化剂(Pt-O3)与另外两种配位结构(Pt-N4和Pt-O2)相比,表现出了更高的催化活性,在烯烃反马氏硼氢化反应中的转化数可达到3288.密度泛函理论计算表明,Pt-O3催化剂具有超高活性的主要原因是其在反应相图中具有最低的决速步能垒.

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.