文献类型：期刊文献

英文题名：Aerogel-Anchored Rh-POM for Stable and Highly Branched-Selective Hydroformylation of Alkenes

作者：Shi, Enting[1]; An, Ning[1]; Wang, Haijing[2]; Zhao, Xiuge[1]; Liao, Huiying[1]; An, Pengfei[3]; Hou, Zhenshan[1]

机构：[1] State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Research Institute of Industrial Catalysis, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China; [2] State Key Laboratory of Petroleum Molecular & Process Engineering, SINOPEC Research Institute of Petroleum Processing Co., Ltd., Beijing, 100083, China; [3] Institute of High Energy Physics, Chinese Academy of Sciences, Beijing Synchrotron Radiation Facility [BSRF], Beijing, 100049, China

年份：2026

外文期刊名：SSRN

收录：EI(收录号：20260397608)

语种：英文

外文关键词：Aerogels - Aldehydes - Aromatization - Binding energy - Catalysis - Catalyst selectivity - Coordination reactions - Economic geology - Hydrocarbons - Hydroformylation - Leaching - Polyoxometalates - Rhodium - Rhodium alloys - Rhodium compounds

摘要：Hydroformylation is one of the most important industrial homogeneous catalytic processes. However, conventional homogeneous rhodium-based catalysts suffer from challenges such as difficult separation and severe leaching of precious metals. Most studies on selective hydroformylation have focused on linear aldehydes, while research on enhancing branched aldehyde selectivity remains limited, particularly for achieving high branched to linear ratios in the hydroformylation of high-value aromatic alkenes such as styrene and its derivatives. In response, this study reports the design and synthesis of a Rh-based polyoxometalate (Rh-POM) heterogeneous catalyst encapsulated in a Schiff-base-rich silicon-based aromatic aerogel. This catalyst exhibits excellent branched selectivity in the hydroformylation of styrene, achieving a branched to linear (B/L) ratio of up to 42.1. Characterization results reveal that, under reaction conditions, the abundant Schiff-base groups in the aerogel framework coordinate with the Rh species of the polyoxometalate clusters, thereby tuning the coordination environment of Rh and the binding mode of the substrate to steer the hydrogenation step toward a Markovnikov-type (branched) addition pathway. Additionally, the anchoring of Rh by the framework of POM and the Schiff-base groups not only prevents Rh aggregation but also weakens the strong Rh-CO coordination, significantly suppressing precious metal leaching. This sheds light on the preparation of stable catalysts. ? 2026, The Authors. All rights reserved.