Modulating the density of catalytic sites in multiple-component covalent organic frameworks for electrocatalytic carbon dioxide reduction

Minghao Liu, Xingyue Zhao, Shuai Yang, Xiubei Yang, Xuewen Li, Jun He, George Zheng Chen, Qing Xu, Gaofeng Zeng

Research output: Journal PublicationArticlepeer-review

5 Citations (Scopus)

Abstract

It is generally assumed that the more metal atoms in covalent organic frameworks (COFs) contribute to higher activity toward electrocatalytic carbon dioxide reduction (CO2RR) and hindered us in exploring the correlation between the density of catalytic sites and catalytic performances. Herein, we have constructed quantitative density of catalytic sites in multiple COFs for CO2RR, in which the contents of phthalocyanine (H2Pc) and nickel phthalocyanine (NiPc) units were preciously controlled. With a molar ratio of 1/1 for the H2Pc and NiPc units in COFs, the catalyst achieved the highest selectivity with a carbon monoxide Faradaic efficiency (FECO) of 95.37% and activity with a turnover frequency (TOF) of 4713.53 h-1. In the multiple H2Pc/NiPc-COFs, the electron-donating features of the H2Pc units provide electron transport to the NiPc centers and thus improved the binding ability of CO2 and intermediates on the NiPc units. The theoretical calculation further confirmed that the H2Pc units donated their electrons to the NiPc units in the frameworks, enhanced the electron density of the Ni sites, and improved the binding ability with Lewis acidic CO2 molecules, thereby boosting the CO2RR performance. This study provides us with new insight into the design of highly active catalysts in electrocatalytic systems.

Original languageEnglish
Pages (from-to)44384-44393
Number of pages10
JournalACS applied materials & interfaces
Volume15
Issue number37
DOIs
Publication statusPublished - 20 Sept 2023

Keywords

  • alternate structure
  • carbon dioxide reduction reaction
  • covalent organic frameworks
  • phthalocyanine
  • structure−property correlation

ASJC Scopus subject areas

  • General Materials Science

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