Premium
Reordering d Orbital Energies of Single‐Site Catalysts for CO 2 Electroreduction
Author(s) -
Han Jianyu,
An Pengfei,
Liu Shuhu,
Zhang Xiaofei,
Wang Dawei,
Yuan Yi,
Guo Jun,
Qiu Xueying,
Hou Ke,
Shi Lin,
Zhang Yin,
Zhao Shenlong,
Long Chang,
Tang Zhiyong
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201907399
Subject(s) - overpotential , catalysis , atomic orbital , active site , porphyrin , faraday efficiency , materials science , molecule , metal , nanotechnology , chemistry , chemical physics , photochemistry , physics , electrochemistry , electrode , organic chemistry , quantum mechanics , metallurgy , electron
The single‐site catalyst (SSC) characteristic of atomically dispersed active centers will not only maximize the catalytic activity, but also provide a promising platform for establishing the structure–activity relationship. However, arbitrary arrangements of active sites in the existed SSCs make it difficult for mechanism understanding and performance optimization. Now, a well‐defined ultrathin SSC is fabricated by assembly of metal‐porphyrin molecules, which enables the precise identification of the active sites for d‐orbital energy engineering. The activity of as‐assembled products for electrocatalytic CO 2 reduction is significantly promoted via lifting up the energy level of metal dz2orbitals, exhibiting a remarkable Faradaic efficiency of 96 % at the overpotential of 500 mV. Furthermore, a turnover frequency of 4.21 s −1 is achieved with negligible decay over 48 h.