Ordered Mesopore Confined Pt Nanoclusters Enable Unusual Self-Enhancing Catalysis

As an important kind of emerging heterogeneous catalyst for sustainable chemical processes, supported metal cluster (SMC) catalysts have received great attention for their outstanding activity; however, the easy aggregation of metal clusters due to their migration along the substrate's surface usually deteriorates their activity and even causes catalyst failure during cycling. Herein, stable Pt nanoclusters (NCs, ∼1.06 nm) are homogeneously confined in the uniform spherical mesopores of mesoporous titania (mpTiO₂) by the interaction between Pt NCs and metal oxide pore walls made of polycrystalline anatase TiO₂. The obtained Pt-mpTiO₂ exhibits excellent stability with well-retained CO conversion (∼95.0%) and Pt NCs (∼1.20 nm) in the long term water-gas shift (WGS) reaction. More importantly, the Pt-mpTiO₂ displays an unusual increasing activity during the cyclic catalyzing WGS reaction, which was found to stem from the in situ generation of interfacial active sites (Ti³⁺-O_v-Pt^δ+) by the reduction effect of spillover hydrogen generated at the stably supported Pt NCs. The Pt-mpTiO₂ catalysts also show superior performance toward the selective hydrogenation of furfural to 2-methylfuran. This work discloses an efficient and robust Pt-mpTiO₂ catalyst and systematically elucidates the mechanism underlying its unique catalytic activity, which helps to design stable SMC catalysts with self-enhancing interfacial activity in sustainable heterogeneous catalysis.