Microwave-Assisted Construction of Acid-Base Cooperative Layered Heterogeneous Catalysts for Dehydrogenative Coupling...

The dehydrogenative coupling of silanes with alcohols represents an atom-economical and environmentally benign approach for the synthesis of organosilicon, which are widely utilized in organic synthesis, surface modification, and functional material design. In response to the demand for efficient and sustainable catalytic systems, this study reports the innovative construction of a series of layered W_XS₂ catalysts featuring acid-base cooperative catalytic sites. A microwave-assisted calcination strategy was employed to achieve precise modulation of the acid and base active sites, enabling structural and functional tunability. Comprehensive characterization revealed that the W⁶⁺/W⁴⁺ ratio plays a pivotal role in determining the surface acidity of the catalysts. Moreover, pyridine and pyrrole poisoning experiments were conducted to clarify the cooperative effect between acidic and basic sites in governing both catalytic activity and selectivity. Isotope-labeling experiments with ¹⁸O further unveiled the mechanistic impact of acid-base site ratios on the reaction pathway, and a dual-site catalytic mechanism was proposed, in which acidic sites activate Si-H bonds while basic sites enhance the nucleophilicity of alcohols. These insights collectively provide a theoretical foundation and practical guidance for the development of high-performance, non-noble-metal catalytic systems for silane transformations.