Design and engineering of microenvironments of supported catalysts toward more efficient chemical synthesis.

Catalytic species such as molecular catalysts and metal catalysts are commonly attached to varieties of supports to simplify their separation and recovery and accommodate various reaction conditions. The physicochemical microenvironments surrounding catalytic species play an important role in catalytic performance, and the rational design and engineering of microenvironments can achieve more efficient chemical synthesis, leading to greener and more sustainable catalysis. In this review, we highlight recent works addressing the topic of the design and engineering of microenvironments of supported catalysts, including supported molecular catalysts and supported metal catalysts. Six types of materials, including oxide nano/microparticle, mesoporous silica nanoparticle (MSN), polymer nanomaterial, reticular material, zeolite, and carbon-based nanomaterial, are widely used as supports for the immobilization of catalytic species. We summarize and discuss the synthesis and modification of supports and the positive effects of microenvironments on catalytic properties such as metal-support interaction, molecular recognition, pseudo-solvent effect, regulating mass transfer, steric effect, etc. These design principles and engineering strategies allow access to a better understanding of structure-property relationships and advance the development of more efficient catalytic processes.