Stabilizing Few‐Atom Platinum Clusters by Zinc Single‐Atom‐Glue for Efficient Anti‐Markovnikov Alkene Hydrosilylation

Abstract

Few‐atom metal clusters (FAMCs) exhibit superior performance in catalyzing complex molecular transformations due to their special spatial environments and electronic states, compared to single‐atom catalysts (SACs). However, achieving the efficient and accurate synthesis of FAMCs while avoiding the formation of other species, such as nanoparticles and SACs, still remains challenges. Herein, we report a two‐step strategy for synthesis of few‐atom platinum (Pt) clusters by predeposition of zinc single‐atom‐glue (Zn1) on MgO nanosheets (Ptn‐Zn1/MgO), where FAMCs can be obtained over a wide range of Pt contents (0.09 to 1.45 wt%). Zn atoms can act as Lewis acidic sites to allow electron transfer between Zn and Pt through bridging O atoms, which play a crucial role in the formation and stabilization of few‐atom Pt clusters. Ptn‐Zn1/MgO exhibited a high selectivity of 93% for anti‐Markovnikov alkene hydrosilylation. Moreover, an excellent activity with a turnover frequency of up to 1.6 ×104 h−1 can be achieved, exceeding most of the reported Pt SACs. Further theoretical studies revealed that the Pt atoms in Ptn‐Zn1/MgO possess moderate steric hindrance, which enables high selectivity and activity for hydrosilylation. This work presents some guidelines for utilizing atomic‐scale species to increase the synthesis efficiency and precision of FAMCs.