Photocatalytic precise hydrogenation of furfural over ultrathin Pt/NiMg-MOF-74 nanosheets: Synergistic effect of surface optimized NiII sites and Pt clusters

Optimizing the electronic structure of the surface active sites and introducing functional sites for a photocatalyst are effective strategies to achieve the photocatalytic selective hydrogenation of biomass. Herein, Pt clusters/bimetallic NiMg-MOF-74 (MNM) ultrathin nanosheets were constructed for the photocatalytic precise hydrogenation of furfural (FUR) to furfuryl alcohol (FAL). A representative sample (Pt/MNM-0.25) shows 99.9% conversion of FUR and 99.9% selectivity of FAL. The electron density of surface coordinatively unsaturated NiII atoms in MNM is decreased after the doping of Mg. In situ ATR-IR indicated that the optimized surface NiII sites induced a more effective coordination activation of FUR molecules via the Ni-η1-(O)-furfural coordination. Electrochemical measurements and in situ EPR results reveal that Pt clusters are the functional surface sites for transferring the photogenerated electrons and dissociating H2. The synergistic effect of surface optimized NiII sites and Pt clusters is emphasized. This work successfully achieves the high-efficiency precise hydrogenation of FUR to FAL via designing surface functionalized Pt clusters/bimetallic MOF ultrathin nanosheets.