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Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO 2 Reduction
Author(s) -
Lu Meng,
Zhang Mi,
Liu ChunGuang,
Liu Jiang,
Shang LinJie,
Wang Min,
Chang JiaNan,
Li ShunLi,
Lan YaQian
Publication year - 2021
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.202011722
Subject(s) - electrocatalyst , covalent bond , covalent organic framework , density functional theory , catalysis , selectivity , faraday efficiency , chemistry , materials science , chemical engineering , nanotechnology , electrochemistry , computational chemistry , organic chemistry , electrode , engineering
In this work, we rationally designed a series of crystalline and stable dioxin‐linked metallophthalocyanine covalent organic frameworks (COFs; MPc‐TFPN COF, M=Ni, Co, Zn) under the guidance of reticular chemistry. As a novel single‐site catalysts (SSCs), NiPc/CoPc‐TFPN COF exhibited outstanding activity and selectivity for electrocatalytic CO 2 reduction (ECR; Faradaic efficiency of CO (FE CO )=99.8(±1.24) %/ 96.1(±1.25) % for NiPc/CoPc‐TFPN COF). More importantly, when coupled with light, the FE CO and current density ( j CO ) were further improved across the applied potential range (−0.6 to −1.2 V vs. RHE) compared to the dark environment for NiPc‐TFPN COF ( j CO increased from 14.1 to 17.5 A g −1 at −0.9 V; FE CO reached up to ca. 100 % at −0.8 to −0.9 V). Furthermore, an in‐depth mechanism study was established by density functional theory (DFT) simulation and experimental characterization. For the first time, this work explored the application of COFs as photo‐coupled electrocatalysts to improve ECR efficiency, which showed the potential of using light‐sensitive COFs in the field of electrocatalysis.