Tailoring CuNi heteronuclear diatomic catalysts:Precision in structural design for exceptionally selective CO2 photoreduction to ethanol
The photocatalytic reduction of CO2 to ethanol has attracted extensive attention,particularly for intricate C-C coupling.In this study,we propose a synthetic pathway for asymmetric CuNi hetero-nuclear diatoms(CuNi HDAs)by anchoring single Cu atoms on the Ni sites of(Ni,Zr)-UiO-66-NH2 to enhance C-C coupling.Cu-(Ni,Zr)-UiO-66-NH2 efficiently performs photocatalytic CO2 conversion with a mass-specific activity(selectivity)of 3218 μmol·gcu-1·h1(97.3％).Spectroscopic analyses and density functional theory calculations revealed that CuNi HDAs with an asymmetric electronic dis-tribution facilitated the activation of CO2 molecules and lowered the C-C coupling barrier energy,thus promoting the formation of*OCCHO intermediates.This,in turn,led to a significant enhance-ment of ethanol selectivity.Furthermore,with interfacial Cu-Ni-O bonds as a rapid electron transport channel,CuNi HDAs enrich enough electrons for 12-electron CO2 reduction,thereby en-hancing ethanol productivity.This study provides a novel strategy for designing highly selective photocatalysts for CO2 conversion at the atomic scale.
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