Structure–Reactivity Relationship of Zeolite-Confined Rh Catalysts for Hydroformylation of Linear α-Olefins

Substituting the molecular metal complexes used in the industrial olefin hydroformylation process is of great significance in fundamental research and practical application. One of the major difficulties in replacing the classic molecular metal catalysts with supported metal catalysts is the low chemoselectivity and regioselectivity of the supported metal catalysts because of the lack of a well-defined coordination environment of the metal active sites. In this work, we have systematically studied the influences of key factors (crystallinity, alkali promoters, etc.) of the Rh-MFI zeolite catalysts on their performances for the hydroformylation of long-chain α-olefins (LAOs). With the help of comprehensive spectroscopy and electron microscopy characterization results, we can correlate the structural features of various Rh-MFI catalysts and their catalytic performances. The resultant structure-reactivity relationship guides us to prepare a nanosized Rh-MFI catalyst, which exhibits about a 3-fold improvement in specific activity compared to the Rh-MFI catalyst with conventional crystallite sizes and maintains very high regioselectivity for hydroformylation of LAOs.