The mechanism of MOF as a heterogeneous catalyst for propene hydroformylation: a DFT study

Abstract

A metal–organic framework composed of a metal center and organic linkers possesses a similar structure to that of a homogeneous metal-complex catalyst for hydroformylation; thus, it could be potentially used as a heterogeneous catalyst for this reaction. In this study, for the first time, we explored the possibility of an MOF with coordinate unsaturated metal sites as the heterogeneous catalyst of propene hydroformylation. A density functional theory (DFT) calculations were used to study the mechanism of propene hydroformylation catalyzed by M–Cu–BTC (M = Rh, Ir). The calculation results indicated that Rh–Cu–BTC and Ir–Cu–BTC can be potential catalysts for olefin hydroformylation. The reaction included three elementary steps: the insertion of H atom into alkene, carbonylation, and the addition of H₂. For a linear pathway, the H₂ addition is the rate-limiting step, while for a branched path, the carbonylation step is the rate-controlling step. The electronic property of the metal center is verified to theoretically have correlations with regioselectivity.