Selective coordination activation regulating the selectivity for photocatalytic hydrogenation of α, β-unsaturated aldehyde over Pd/MIL-100(FeaCub)

Abstract

Here, the mixed metal nodes MOFs, Pd/MIL-100(FeaCub), were constructed as photocatalysts for hydrogenation of α, β-unsaturated aldehyde (UAL) under visible light. 1 wt% Pd/MIL-100(Fe0.81Cu0.19) can convert a range of UAL to saturated aldehydes (SAL) with a high efficiency (≈ 100 %) and selectivity (≈ 98 %). The results of XPS and in situ DRIFTS reveal that UAL can be selectively activated via a coordination of -CC- on Cu2+ sites, determining the high selectivity of the photocatalytic reaction. The mixed metal nodes and Pd clusters can improve the transformation and separation of photogenerated electrons-holes. EPR result suggests that photogenerated carriers can facilitate the generation of H·on Pd/MIL-100(Fe0.81Cu0.19), enhancing the catalytic activity. A possible mechanism is proposed for elucidating the catalytic processes at the molecular level. This work provides a valuable strategy for tailoring the selectivity of photocatalytic hydrogenation via selective coordination activation.