Confining Molecular rhodium phosphine catalysts within liquid-solid hybrid microreactor for olefin hydroformylation

doi:10.1016/S1872-2067(25)64696-1

Abstract

Abstract:

The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group, which enables us to conveniently bridge the gap between homo- and heterogeneous catalysis. In this study, we extend this general concept to the confinement of molecular rhodium phosphine complexes, including Rh-TPPTS, Rh-TPPMS and Rh-SXP, for olefin hydroformylation reactions. A series of hybrid catalyst materials consisting a modulated liquid interior ([BMIM]NTf₂, [BMIM]PF₆, [BMIM]BF₄ or H₂O) and a permeable silica crust were fabricated through our developed Pickering emulsion-based method, showing 9.4-24.2-fold activity enhancement and significantly improved aldehyde selectivity (from 72.2%, 61.8% to 86.6%) compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene. Interestingly, the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool. The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of oleﬁn substrates and be recycled without a signiﬁcant loss of activity for at least seven times.

Key words: Immobilization, Molecular catalyst, Olefin hydroformylation, Heterogeneous catalysis, Hybrid microreactor

Xiaoting Hao, Qi Liu, Yuwei Wang, Xiaoming Zhang, Hengquan Yang. Confining Molecular rhodium phosphine catalysts within liquid-solid hybrid microreactor for olefin hydroformylation[J]. Chinese Journal of Catalysis, 2025, 73: 261-270.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64696-1

https://www.cjcatal.com/EN/Y2025/V73/I6/261

Figures/Tables 6

Scheme 1. Schematic illustration of the construction of liquid-solid hybrid microreactors confining with molecular rhodium phosphine complexes for hydroformylation catalysis.

Fig. 1. Characterizations of the Pickering droplets and their derived liquid-solid hybrid microreactors. (a) Optical microscopy image of the formulated Pickering droplets and their size distribution cartogram ([BMIM]PF6 as the IL phase). (b) Fluorescence microscopy observation dyeing with Rhodamine B, inset shows a 3D image. SEM images of the hybrid microreactor: a low magnified observation (inset shows the decorated silica emulsifier) (c), an individual broken particle (d), and a cross-sectional image of the outer crust (e). (f) TEM image of a crust segment. (g) Element mappings, including Si, O, N, F, P and Rh. (h) TGA curve. (i,j) N2 sorption isotherms and the BJH pore size distribution. (k,l) SEM images the hybrid microreactors with different capsule size and crust thickness. (m) Statistics of the particle size and crust thickness of other liquid based hybrid microreactors.

Fig. 2. Structural stability and molecular permeability of the liquid-solid hybrid microreactors. (a,b) Appearance and optical micrographs of the liquid-solid hybrid microreactor and Pickering droplet in nonpolar 1-dodecene and polar tridecanal surroundings at varied temperatures. (c) Time-dependent confocal fluorescence microscopy images of the diffusion of Nile Red (8 μmol L?1 in n-octane), and the corresponding fluorescence intensity variations along with time. Scale bar = 20 μm.

Fig. 3. Catalytic performance of the liquid-solid hybrid microreactor in olefin hydroformylation reactions. Kinetic plots (a1), TOF values (a2) and aldehyde selectivities (a3) for different catalytic systems. Hybrid microreactors (i) is shown in blue, SBA-15-SIL-23 wt% (ii) in orange, Pickering emulsions (iii) in red, SBA-15-SIL-48 wt% (iv) in green and biphasic system (v) in black. Kinetic plots (b1,c1), TOF values (b2,c2) and aldehyde selectivities (b3, c3) for the hybrid microreactor with different capsule size and crust thickness. Reaction conditions: 1.0 g hybrid catalyst that containing 10 μmol rhodium, 10 mmol 1-dodecene in 5 mL toluene, 110 °C, 3 MPa CO/H2.

Fig. 4. Modulation of the liquid-solid hybrid microreactor for optimizing the olefin hydroformylation reactions. (a1-a3) Kinetic plots, TOF values and aldehyde selectivities of the hybrid microreactors with varied liquid pools. (b1-b3) Kinetic plots, TOF and aldehyde selectivities of the hybrid microreactors with different Rh catalytic species. (c1-c2, d1-d2) Kinetic plots and aldehyde selectivities of the hybrid microreactors under different reaction conditions.

Fig. 5. Recyclability and substrate expansion of the hybrid microreactor catalyst in hydroformylation reactions. (a) Recyclability of the hybrid catalyst. (b,c) SEM image and TGA curve of the hybrid microreactor after recycling tests. (d) Substrate expansion of the hybrid microreactor in hydroformylation of various olefins.

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