期刊
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
卷 10, 期 47, 页码 15467-15479出版社
AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.2c04674
关键词
heterogeneous catalysis; rhodium; single-metal-site catalysts; electronegativity; coordination state
资金
- National Natural Science Foundation of China [22002152, 22108275]
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDA 21020900, XDA29050300]
- Youth Innovation Promotion Association CAS [2021181]
- Natural Science Foundation of Liaoning Province [2022-MS-021]
- Dalian Young Star of Science and Technology Project [2021RQ107]
In this study, a series of Rh-based single-metal-site catalysts were designed and synthesized on porous organic polymers with different electro-negativities. The modification of Rh-P active sites with functional groups promoted the formation of active species and the insertion of substrates, leading to improved catalytic activity, selectivity, l/b ratio, and stability. Various characterization techniques and theoretical calculations were used to gain further insights into the microenvironment and active structure of the catalysts.
To enhance the catalytic performance of single-metal-site catalysts (SMSCs), regulating the interaction between the active site and substrate is crucial but challenging. Herein, a series of Rh-based SMSCs (Rh/m-3vPAr3-POLs) were designed and synthesized on P-abundant porous organic polymers (POPs) with different electro-negativities of frame phosphine. The Rh-P active sites on various POPs were modified by functional groups (-F, -H, -Me, or -OMe). Both the formation of HRh(CO)2(P)2 active species and the insertion of CO were promoted via the electron-accepting property of fluorine, which endowed Rh/m-3vPAr3-POL-F with the best activity (TOF = 3000 h-1), selectivity (>88.1%), l/b ratio (>6.8), and stability (1000 h) for 1-octene hydroformylation in a fixed-bed reactor. Multiple characterization techniques (extended X-ray absorption fine structure, scanning transmission electron microscopy, in situ Fourier-transform infrared spectroscopy, etc.) and density functional theory calculations were employed to get further insights into the microenvironment and active structure of Rh-based SMSCs. This work offers a promising avenue for designing efficient and stable SMSCs in heterogeneous catalysis.
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