Grain Boundary‐Rich Copper Nanocatalysts Generated from Metal‐Organic Framework Nanoparticles for CO2‐to‐C2+ Electroconversion

Abstract Due to severe contemporary energy issues, generating C2+ products from electrochemical carbon dioxide reduction reactions (eCO2RRs) gains much interest. It is known that the catalyst morphology and active surface structures are critical for product distributions and current densities. Herein, a synthetic protocol of nanoparticle morphology on copper metal‐organic frameworks (n‐Cu MOFs) is developed by adjusting growth kinetics with termination ligands. Nanoscale copper oxide aggregates composed of small particulates are yielded via calcining the Cu‐MOF nanoparticles at a specific temperature. The resulting nanosized MOF‐derived catalyst (n‐MDC) exhibits Faradaic efficiencies toward ethylene and C2+ products of 63% and 81% at −1.01 V versus reversible hydrogen electrode (RHE) in neutral electrolytes. The catalyst also shows prolonged stability for up to 10 h. A partial current density toward C2+ products is significantly boosted to −255 mA cm−2 in an alkaline flow cell system. Comprehensive analyses reveal that the nanoparticle morphology of pristine Cu MOFs induces homogeneous decomposition of organic frameworks at a lower calcination temperature. It leads to evolving grain boundaries in a high density and preventing severe agglomeration of copper domains, the primary factors for improving eCO2RR activity toward C2+ production.