The mechanism of MOF as a heterogeneous catalyst for propene hydroformylation: a DFT study,Reaction Chemistry & Engineering

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The mechanism of MOF as a heterogeneous catalyst for propene hydroformylation: a DFT study
Reaction Chemistry & Engineering ( IF 3.4 ) Pub Date : 2022-01-11 , DOI: 10.1039/d1re00527h
Yifei Chen _{1,

2} , Yang Gao _{1,

2} , Lingtao Wang _{1,

2} , Hao Gong _{1,

2}

Affiliation

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.

中文翻译：

MOF作为丙烯羰基化非均相催化剂的机理：DFT研究

由金属中心和有机连接体组成的金属-有机骨架具有与用于加氢甲酰化的均相金属络合物催化剂相似的结构；因此，它可以潜在地用作该反应的非均相催化剂。在这项研究中，我们首次探索了具有配位不饱和金属位点的 MOF 作为丙烯加氢甲酰化非均相催化剂的可能性。使用密度泛函理论 (DFT) 计算来研究 M-Cu-BTC (M = Rh, Ir) 催化的丙烯羰基化机理。计算结果表明，Rh-Cu-BTC 和 Ir-Cu-BTC 可以作为烯烃加氢甲酰化的潜在催化剂。该反应包括三个基本步骤：将 H 原子插入烯烃、羰基化和添加 H ₂. 对于线性路径，H ₂添加是限速步骤，而对于分支路径，羰基化步骤是速率控制步骤。验证了金属中心的电子特性理论上与区域选择性相关。

更新日期：2022-01-11

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