Grain Boundary-Rich Copper Nanocatalysts Generated from Metal-Organic Framework Nanoparticles for CO 2 -to-C 2+ Electroconversion.

Due to severe contemporary energy issues, generating C 2+ products from electrochemical carbon dioxide reduction reactions (eCO 2 RRs) 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 C 2+ 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 C 2+ 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 eCO 2 RR activity toward C 2+ production.