Maximizing Electroactive Sites in a Three‐Dimensional Covalent Organic Framework for Significantly Improved Carbon Dioxide Reduction Electrocatalysis

Abstract

AbstractSynthesis of functional 3D COFs with irreversible bond is challenging. Herein, 3D imide‐bonded COFs were constructed via the imidization reaction between phthalocyanine‐based tetraanhydride and 1,3,5,7‐tetra(4‐aminophenyl)adamantine. These two 3D COFs are made up of interpenetratedptsnetworks according to powder X‐ray diffraction and gas adsorption analyses. CoPc‐PI‐COF‐3 doped with carbon black has been employed to fabricate the electrocatalytic cathode towards CO2reduction reaction within KHCO3aqueous solution, displaying the Faradaic efficiency of 88–96 % for the CO2‐to‐CO conversion at the voltage range of ca. −0.60 to −1.00 V (vs. RHE). In particular, the 3D porous structure of CoPc‐PI‐COF‐3 enables the active electrocatalytic centers occupying 32.7 % of total cobalt‐phthalocyanine subunits, thus giving a large current density (jCO) of −31.7 mA cm−2at −0.90 V. These two parameters are significantly improved than the excellent 2D COF analogue (CoPc‐PI‐COF‐1, 5.1 % and −21.2 mA cm−2).