Stable Dioxin‐Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo‐Coupled Electrocatalysts for CO2Reduction

Abstract 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.