Elaborate Modulating Binding Strength of Intermediates via Three‐component Covalent Organic Frameworks for CO2 Reduction Reaction

A three-component covalent organic framework (COF) was constructed with electron-rich diarylamine unit and electron-deficient benzothiazole and Co-porphyrin units, thus overcoming the weak or strong interactions between COFs and intermediates, improving the electrocatalytic CO₂ reduction reaction (CO₂RR) performance.

Abstract

The catalytic performance for electrocatalytic CO₂ reduction reaction (CO₂RR) depends on the binding strength of the reactants and intermediates. Covalent organic frameworks (COFs) have been adopted to catalyze CO₂RR, and their binding abilities are tuned via constructing donor-acceptor (DA) systems. However, most DA COFs have single donor and acceptor units, which caused wide-range but lacking accuracy in modulating the binding strength of intermediates. More elaborate regulation of the interactions with intermediates are necessary and challenge to construct high-efficiency catalysts. Herein, the three-component COF with D-A-A units was first constructed by introducing electron-rich diarylamine unit, electron-deficient benzothiazole and Co-porphyrin units. Compared with two-component COFs, the designed COF exhibit elevated electronic conductivity, enhanced reducibility, high efficiency charge transfer, further improving the electrocatalytic CO₂RR performance with the faradic efficiency of 97.2 % at −0.8 V and high activity with the partial current density of 27.85 mA cm⁻² at −1.0 V which exceed other two-component COFs. Theoretical calculations demonstrate that catalytic sites in three-component COF have suitable binding ability of the intermediates, which are benefit for formation of *COOH and desorption of *CO. This work offers valuable insights for the advancement of multi-component COFs, enabling modulated charge transfer to improve the CO₂RR activity.

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