Molecular Engineering of Copper Phthalocyanine for CO2 Electroreduction to Methane

Abstract Efficient electrochemical CO 2 reduction reaction (ECO 2 RR) to multi‐electron reductive products remains a great challenge. Herein, molecular engineering of copper phthalocyanines (CuPc) was explored by modifying electron‐withdrawing groups (EWGs) (cyano, sulfonate anion) and electron‐donating groups (EDGs) (methoxy, amino) to CuPc, then supporting onto carbon paper or carbon cloth by means of droplet coating, loading with carbon nanotubes and coating in polypyrrole (PPy). The results showed that the PPy‐coated CuPc effectively catalysed ECO 2 RR to CH 4 . Interestingly, experimental results and DFT calculations indicated EWGs markedly improved the selectivity of methane for the reason that the introduction of EWGs reduces electron density of catalytic active center, resulting in a positive move to initial reduction potential. Otherwise, the modification of EDGs significantly reduces the selectivity towards methane. This electronic effect and heterogenization of CuPc are facile and effective molecular engineering, benefitting the preparation of electrocatalysts for further reduction of CO 2 .