单独一对
催化作用
分解
钴
共价键
选择性
材料科学
电子结构
共价有机骨架
硫黄
化学
分子
计算化学
无机化学
有机化学
作者
Qianjun Zhi,Rong Jiang,Xiya Yang,Yucheng Jin,Dongdong Qi,Kang Wang,Yunpeng Liu,Jianzhuang Jiang
标识
DOI:10.1038/s41467-024-44899-8
摘要
Abstract Realization of stable and industrial-level H 2 O 2 electroproduction still faces great challenge due large partly to the easy decomposition of H 2 O 2 . Herein, a two-dimensional dithiine-linked phthalocyaninato cobalt (CoPc)-based covalent organic framework (COF), CoPc-S-COF, was afforded from the reaction of hexadecafluorophthalocyaninato cobalt (II) with 1,2,4,5-benzenetetrathiol. Introduction of the sulfur atoms with large atomic radius and two lone-pairs of electrons in the C-S-C linking unit leads to an undulated layered structure and an increased electron density of the Co center for CoPc-S-COF according to a series of experiments in combination with theoretical calculations. The former structural effect allows the exposition of more Co sites to enhance the COF catalytic performance, while the latter electronic effect activates the 2e − oxygen reduction reaction (2e − ORR) but deactivates the H 2 O 2 decomposition capability of the same Co center, as a total result enabling CoPc-S-COF to display good electrocatalytic H 2 O 2 production performance with a remarkable H 2 O 2 selectivity of >95% and a stable H 2 O 2 production with a concentration of 0.48 wt% under a high current density of 125 mA cm −2 at an applied potential of ca . 0.67 V versus RHE for 20 h in a flow cell, representing the thus far reported best H 2 O 2 synthesis COFs electrocatalysts.
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