固液杂化微反应器限域铑膦配合物催化烯烃氢甲酰化反应

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

催化学报 ›› 2025, Vol. 73: 261-270.DOI: 10.1016/S1872-2067(25)64696-1

固液杂化微反应器限域铑膦配合物催化烯烃氢甲酰化反应

郝晓婷^a^,^b, 刘琪^a, 王雨薇^a^,^b, 张晓明^a^,^b(), 杨恒权^a()

^a山西大学化学化工学院, 煤基高端化学品绿色催化合成山西省重点实验室, 山西太原 030006
^b河南大学化学与分子科学学院, 龙子湖新能源实验室, 河南开封 475004

收稿日期:2024-12-19 接受日期:2025-03-09 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: xmzhang@henu.edu.cn (张晓明),hqyang@sxu.edu.cn (杨恒权).
基金资助:
山西省优秀青年基金(202103021222003);国家自然科学基金(22072078);国家自然科学基金(21925203)

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

Xiaoting Hao^a^,^b, Qi Liu^a, Yuwei Wang^a^,^b, Xiaoming Zhang^a^,^b(), Hengquan Yang^a()

^aShanxi Key Laboratory of Coal-based Value-added Chemicals Green Catalysis Synthesis, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, Shanxi, China
^bLongzihu New Energy Laboratory, College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, Henan, China

Received:2024-12-19 Accepted:2025-03-09 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: xmzhang@henu.edu.cn (X. Zhang),hqyang@sxu.edu.cn (H. Yang).
Supported by:
Outstanding Youth Fund of Shanxi Province(202103021222003);Natural Science Foundation of China(22072078);Natural Science Foundation of China(21925203)

摘要/Abstract

摘要：

烯烃氢甲酰化反应是工业合成醛类化合物最重要的方法之一. 铑膦配合物是最为常用的一类均相催化剂, 具有反应活性高、选择性好等优点, 但面临着产物分离、催化剂循环使用和连续化生产等挑战. 相较而言, 多相催化具有催化剂易与反应体系分离、实现连续化操作等优势. 因而, 将均相氢甲酰化催化剂多相化, 形成兼具均相和多相双重优势的催化新体系是解决上述问题的重要手段.

本文针对离子液介质的烯烃氢甲酰化反应过程, 构建了固液杂化催化体系. 以Pickering乳液为模板, 通过乳液界面处硅烷偶联剂的溶胶-凝胶过程, 成功构筑了离子液体核@氧化硅壳的固液杂化微反应器, 实现了铑基分子催化剂在微反应器内的原位封装. 通过内部离子液体种类的调控, 获得了不同微化学环境(包括[BMIM]PF₆, [BMIM]NTf₂和[BMIM]BF₄等)的微反应器; 通过控制Pickering乳液的尺寸、交联剂的用量, 实现了微反应器尺寸(12-53 μm)、壳层厚度(60-170 nm)的调控; 同时, 热稳定性和溶剂耐受性实验证实了材料良好的热稳定性与溶剂耐受性, 并通过荧光分子探针渗透性实验验证了微反应器的分子快速扩散和交换能力. 所构建的固液杂化微反应器具有增大的液-液反应界面, 且分子催化剂为“自由状态”, 在长链1-十二烯氢甲酰化反应中, 该微反应器达到了99.7%的转化率和86.8%的醛选择性(醛正异构比n/b = 3.1), 优于传统负载离子液体系、Pickering乳液和传统两相体系. 通过对液体核种类、微反应器颗粒尺寸、壳层厚度和内部分子催化剂种类等参数的调控, 实现了催化剂反应性能的调控和优化, 并初步获得了相应的催化剂结构和反应性能之间的构效关系. 通过研究金属铑配体的组成, 发现以双齿SXP配体、P/Rh = 10的条件下, 在1-十二烯氢甲酰化反应中, 10 h反应转化率达99%以上, 醛选择性为93.1%, 醛正异构比为38.3. 所构筑的固液杂化微反应器具有良好的底物适用性, 能够应用于1-十八烯、1-癸烯、1-辛烯和1-庚烯等底物中. 此外, 所制备的微反应器具有较好的稳定性, 能够循环反应7次以上, X射线光电子能谱和固体P核磁表征表明, 反应后催化剂活性和选择性下降可能与Rh-配体配位减弱或SXP配体的部分氧化分解有关.

综上所述, 本文利用固体壳层限域的微空间, 将均相离子液体催化体系分散为无数微小的液滴, 使得反应过程从微观上来看为均相催化, 但宏观上又具有固体材料可循环使用的优势, 为实现均相和多相氢甲酰化催化的融合发展提供了新的方法和途径.

关键词: 均多相融合, 分子催化剂限域, 烯烃氢甲酰化反应, 多相化, 杂化微反应器

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

郝晓婷, 刘琪, 王雨薇, 张晓明, 杨恒权. 固液杂化微反应器限域铑膦配合物催化烯烃氢甲酰化反应[J]. 催化学报, 2025, 73: 261-270.

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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图/表 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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固液杂化微反应器限域铑膦配合物催化烯烃氢甲酰化反应

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

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