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Abstract: Capped chelating organic molecules are presented as a design principle for tuning heterogeneous nanoparticles for electrochemical catalysis. Gold nanoparticles (AuNPs) functionalized with a chelating tetradentate porphyrin ligand show a 110‐fold enhancement compared to the oleylamine‐coated AuNP in current density for electrochemical reduction of CO2 to CO in water at an overpotential of 340 mV with Faradaic efficiencies (FEs) of 93 %. These catalysts also show excellent stability without deactivation (<5 % productivity loss) within 72 hours of electrolysis. DFT calculation results further confirm the chelation effect in stabilizing molecule/NP interface and tailoring catalytic activity. This general approach is thus anticipated to be complementary to current NP catalyst design approaches. [ABSTRACT FROM AUTHOR]

Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO2 reduction. Palladium functionalized with a chelating tris‐N‐heterocyclic carbene (NHC) ligand (Pd‐timtmbMe) exhibits a 32‐fold increase in activity for electrochemical reduction of CO2 to C1 products with high Faradaic efficiency (FEC1=86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC‐ligated Pd electrode (Pd‐mimtmbMe). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular‐materials interfaces enabled by surface organometallic chemistry. [ABSTRACT FROM AUTHOR]