Enhancing Electroreduction CO2 to Hydrocarbons via Tandem Electrocatalysis by Incorporation Cu NPs in Boron Imidazolate Frameworks

Abstract Due to the higher value of deeply‐reduced products, electrocatalytic CO 2 reduction reaction (CO 2 RR) to multi‐electron‐transfer products has received more attention. One attractive strategy is to decouple individual steps within the complicated pathway via multi‐component catalysts design in the concept of tandem catalysts. Here, a composite of Cu@BIF‐144(Zn) (BIF = boron imidazolate framework) is synthesized by using an anion framework BIF‐144(Zn) as host to impregnate Cu 2+ ions that are further reduced to Cu nanoparticles (NPs) via in situ electrochemical transformation. Due to the microenvironment modulation by functional BH(im) 3 − on the pore surfaces, the Cu@BIF‐144(Zn) catalyst exhibits a perfect synergetic effect between the BIF‐144(Zn) host and the Cu NP guest during CO 2 RR. Electrochemistry results show that Cu@BIF‐144(Zn) catalysts can effectively enhance the selectivity and activity for the CO 2 reduction to multi‐electron‐transfer products, with the maximum FE CH4 value of 41.8% at −1.6 V and FE C2H4 value of 12.9% at −1.5 V versus RHE. The Cu@BIF‐144(Zn) tandem catalyst with CO‐rich microenvironment generated by the Zn catalytic center in the BIF‐144(Zn) skeleton enhanced deep reduction on the incorporated Cu NPs for the CO 2 RR to multi‐electron‐transfer products.