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

Herein, an effective tandem catalysis strategy is developed to improve the selectivity of the CO2RR towards C2H4 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 CO2RR to produce C2H4. The Faradaic efficiency of C2H4 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 CH4 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 C2H4 on the nearby Cu NP sites. The work offers an effective avenue to design electrocatalysts for the highly selective CO2RR to produce multicarbon products via a tandem route. [ABSTRACT FROM AUTHOR]