As part of the heterogeneous catalysis concept, nanoparticle catalysis is the advanced key technology to connect the divergence between classical chemical synthesis methods and environmentally benign sustainable synthesis processes. The demonstration of nanoparticle catalysts for the sustainable and mild synthesis of chemicals is a fast-growing area in catalysis. This chapter will focus on a series of catalytic systems for hydrogen transfer-type or so-called borrowing hydrogen reactions using supported metal catalysts to synthesize chemicals directly and will highlight a group of coupling reactions that generates C-O, C-C, C-N, and C-S bonds. These catalytic coupling reactions possess a general mechanistic aspect: dehydrogenation of poor electrophile alcohols/amines to activated electrophiles, condensation (self or cross or with different nucleophiles), and hydrogenation of condensate. The feasibility of these catalytic coupling reactions is abided with the proper catalyst design where supports are enriched with acidic, basic, or amphoteric properties that promote the condensation reactions, and metal nanoparticle sites are responsible for the hydrogen transfer from the alcohols or amines followed by the re-hydrogenation of the condensation product accordingly. Compared to the state-of-the-art homogeneous catalytic systems, these heterogeneous metal nanoparticle-catalyzed reactions possess catalytic reusability, catalytic efficiency, and sustainability advantages.
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