Highly Selective Tandem Electroreduction of CO2 to Ethylene over Atomically Isolated Nickel–Nitrogen Site/Copper Nanoparticle Catalysts

Abstract Herein, an effective tandem catalysis strategy is developed to improve the selectivity of the CO 2 RR towards C 2 H 4 by multiple distinct catalytic sites in local vicinity. An earth‐abundant elements‐based tandem electrocatalyst PTF(Ni)/Cu is constructed by uniformly dispersing Cu nanoparticles (NPs) on the porphyrinic triazine framework anchored with atomically isolated nickel–nitrogen sites (PTF(Ni)) for the enhanced CO 2 RR to produce C 2 H 4 . The Faradaic efficiency of C 2 H 4 reaches 57.3 % at −1.1 V versus the reversible hydrogen electrode (RHE), which is about 6 times higher than the non‐tandem catalyst PTF/Cu, which produces CH 4 as the major carbon product. The operando infrared spectroscopy and theoretic density functional theory (DFT) calculations reveal that the local high concentration of CO generated by PTF(Ni) sites can facilitate the C−C coupling to form C 2 H 4 on the nearby Cu NP sites. The work offers an effective avenue to design electrocatalysts for the highly selective CO 2 RR to produce multicarbon products via a tandem route.