Docking MOF crystals on graphene support for highly selective electrocatalytic peroxide production  

作　　者：Xiaofeng Huang Peter Oleynikov Hailong He Alvaro Mayoral Linqin Mu Feng Lin Yue-Biao Zhang 

机构地区：[1]School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210,China [2]Department of Chemistry,Virginia Tech,Blacksburg,VA 24061,USA

出　　处：《Nano Research》2022年第1期145-152,共8页纳米研究（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21522105 and 51861145313);the Science&Technology Commission of Shanghai Municipality(17JC1404000);support from the ShanghaiTech-SARI Joint Laboratory of Low-Carbon Energy Science,the Centre for High-resolution Electron Microscopy(ChEM,contract No.EM02161943);the Analytical Instrumentation Center(Contract no.SPST-AIC10112914);support of National Natural Science Foundation of China(Nos.21850410448 and 21835002).

摘　　要：Tailoring the reaction kinetics is the central theme of designer electrocatalysts,which enables the selective conversion of abundant and inert atmospheric species into useful products.Here we show a supporting effect in tuning the electrocatalytic kinetics of oxygen reduction reaction(ORR)from four-electron to two-electron mechanism by docking metalloporphyrin-based metal-organic frameworks(MOFs)crystals on graphene support,leading to highly selective peroxide production with faradaic efficiency as high as 93.4%.A magic angle of 38.1°tilting for the co-facial alignment was uncovered by electron diffraction tomography,which is attributed to the maximization of n-n interaction for mitigating the lattice and symmetry mismatch between MOF and graphene.The facilitated electron migration and oxygen chemisorption could be ascribed to the supportive effect of graphene that disperses of the electron state of the active center,and ultimately regulates rate-determining step.

关 键 词：metal-organic frameworks NANOCOMPOSITES support effect oxygen reduction reaction peroxide selectivity 

分 类 号：O64[理学—物理化学]