Regulating microenvironment of heterogeneous Rh mononuclear complex via sulfur-phosphine co-coordination to enhance the performance of hydroformylation of olefins

doi:10.1016/S1872-2067(25)64795-4

Chinese Journal of Catalysis ›› 2025, Vol. 78: 156-169.DOI: 10.1016/S1872-2067(25)64795-4

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Regulating microenvironment of heterogeneous Rh mononuclear complex via sulfur-phosphine co-coordination to enhance the performance of hydroformylation of olefins

Siquan Feng^a^,¹, Cunyao Li^a^,¹, Yuxuan Zhou^b^,¹, Xiangen Song^a^,^*(), Miao Jiang^a, HuFei Dai^b, Shangsheng Song^a, Benhan Fan^a, Yutong Cai^a^,^c, Bin Li^a, Qiao Yuan^a^,^c, Xingju Li^a, Lei Zhu^a, Yue Zhang^a, Weimiao Chen^a, Tao Liu^a, Li Yan^a^,^*(), Xueqing Gong^d^,^*(), Yunjie Ding^a^,^e^,^*()

^aDalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bSchool of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China
^dSchool of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
^eState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2025-05-20 Accepted:2025-07-03 Online:2025-11-18 Published:2025-10-14
Contact: *E-mail: xiangensong@dicp.ac.cn (X. Song), yanli@dicp.ac.cn (L. Yan), xqgong@sjtu.edu.cn (X. Gong), dyj@dicp.ac.cn (Y. Ding).
About author:¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2023YFA1506604);National Key R&D Program of China(2023YFA1507500);National Natural Science Foundation of China(22002156);National Natural Science Foundation of China(22002152);National Natural Science Foundation of China(22108275);National Natural Science Foundation of China(22372161);Youth Innovation Promotion Association of the Chinese Academy of Sciences(2022179);Youth Innovation Promotion Association of the Chinese Academy of Sciences(2023190);Youth Innovation Promotion Association of the Chinese Academy of Sciences(2021181);Liaoning Provincial Science and Technology Program Joint Program (Technology Tackling Program Project(3E1731683594447);CAS Project for Young Scientists in Basic Research(YSBR-022);Natural Science Foundation of Liaoning Province-Outstanding Youth Science Foundation(2024JH3/10200014);Dalian Outstanding Young Scientific and Technological Talents(2024RY016);and the Foundation of DICP I202117 and DICP I202455.

Abstract

Abstract:

Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins. However, the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mononuclear complex due to the difference of their electronegativities, and coordination capabilities. Herein, we report a novel sulfur-phosphine co-coordinated heterogeneous Rh mononuclear complex catalyst (Rh₁/POPs-PPh₃&S), which exhibits an unexpected 1.5-2.0 times catalytic activity for hydroformylation of olefins (C₃⁼, C₅⁼-C₈⁼), in comparison with the solely phosphine-coordinated Rh mononuclear complex catalyst (Rh₁/POPs-PPh₃). In contrast, sulfur coordination alone leads to severe sulfur poisoning with significantly inhibited catalytic performance. Experimental and theoretical analyses reveal that phosphine coordination promotes catalytic activity via its strong electron-donating ability, while sulfur occupies a coordination site and reduces the electronic density of Rh ions. The synergistical coordination of sulfur and phosphine optimizes the electronic density of active Rh ions and decreases the energy barrier of the rate-determining step of olefin insertion, thus enhancing the hydroformylation activity, regioselectivity and stability of Rh₁/POPs-PPh₃&S.

Key words: Heterogeneous hydroformylation, Rh mononuclear complex, Sulfur-Phosphine co-coordination, Synergistic effect, Sulfur poison, Sulfur promotion, Regulation of microenvironment

Siquan Feng, Cunyao Li, Yuxuan Zhou, Xiangen Song, Miao Jiang, HuFei Dai, Shangsheng Song, Benhan Fan, Yutong Cai, Bin Li, Qiao Yuan, Xingju Li, Lei Zhu, Yue Zhang, Weimiao Chen, Tao Liu, Li Yan, Xueqing Gong, Yunjie Ding. Regulating microenvironment of heterogeneous Rh mononuclear complex via sulfur-phosphine co-coordination to enhance the performance of hydroformylation of olefins[J]. Chinese Journal of Catalysis, 2025, 78: 156-169.

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Figures/Tables 7

Fig. 1. The industrial plant of 50000 tons/year ethylene hydroformylation based on heterogeneous mononuclear Rh1/POPs-PPh3 catalyst at Ningbo Juhua Chemical & Science Co., Ltd., Zhejiang, China in the 2020s, which was developed by Ding’s group of Dalian Institute of Chemical Physicals, Chinese Academy of Science.

Fig. 2. The activity of heterogeneous mononuclear Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S for olefin hydroformylation. (a) Preparation of sulfur- -coordinated Rh-PPh3 (Rh1/POPs-PPh3&S) catalyst. (b) Effect of ratios of sulfur with phosphine on the activity of Rh1/POPs-PPh3&S for propene hydroformylation; 80 °C, 2.0 h, autoclave, C3H6/CO/H2 = 1:1:1, 1.0 MPa, 600 rpm; the ratio of olefin to rhodium is approximately 1500. (c) The activity conversion, n/i values and TOF comparison between Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S for C5H10, C6H12, C7H14, C8H16 hydroformylation; 80 °C, 2.0 h, autoclave, CO/H2 = 1:1, 1.0 MPa; C5H10, C6H12, C7H14, C8H16, 1.0 g, 600 rpm; the ratios of olefin to rhodium are approximately 5868, 4892, 4194 and 3668, respectively. (d) The stability test of Rh1/POPs-PPh3&S for propylene hydroformylation, 120 °C, C3H6/CO/H2 = 1:1:1, 1.0 MPa. (e) The apparent activation energy comparison of the Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts.

Fig. 3. The HAADF-STEM images of spent Rh?/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts, the EXAFS Fourier transform in R space, as well as the wavelet transform. (a) The HAADF-STEM image of spent Rh?/POPs-PPh3t, and (b) Rh1/POPs-PPh3&S. (c) The 31P magic angle spinning solid-state NMR of Rh?/POPs-PPh3 and Rh1/POPs-PPh3&S. (d) The Fourier transform of the EXAFS data in R space of Rh foil, spent Rh?/POPs-PPh3 and Rh1/POPs-PPh3&S. The first shell coordination paths fitting of (e) Rh1/POPs-PPh3&S, and (f) Rh1/POPs-PPh3. The wavelet transforms of (g) Rh1/POPs-PPh3&S, (h) Rh1/POPs-PPh3, and (i) Rh foil.

Fig. 4. The molecular structure identification of the spent Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S (a) The in-situ CO-TPD of Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts after treatment with CO/H2, (b) In-situ DRIFTS spectra of Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts. (c) The XANES comparison of Rh foil, Rh2O3, spent Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts. (d-f) The Rh 3d5/2, P 2p3/2, S 2p3/2 XPS spectra of spent Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts. (g-i) In-situ TPSR-MS signals of m/z = 42 (C3H6), m/z = 28 (CO), and m/z = 2 (H2) from Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts during propylene hydroformylation.

Fig. 5. The reaction process exploration on Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts for propene hydroformylation. (a-c) In-situ TPSR-MS signals of m/z = 72 (C4H8O), m/z = 43 (C3H7) and m/z = 44 (C3H8) from Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts during propylene hydroformylation. (d) The in-situ DRIFTS spectra of propene hydroformylation on Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts.

Fig. 6. The DFT calculated the relative energy of different reaction coordination on the mononuclear Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S catalysts catalyst for propylene hydroformylation.

Fig. 7. The DFT calculation Bader electron analysis. (a) The single-site Rh Bader electron analysis of mononuclear Rh1/POPs-PPh3 and Rh1/POPs-PPh3&S during the reaction pathway (1, 2, 4, 6, 8 are intermediates, and 3, 5, 7, 9 are the corresponding transition states, corresponding olefin insertion, CO carbonyl insertion, H2 oxidative addition and acyl hydrogenolysis, respectively). The all-atom Bader charge analysis of mononuclear Rh1/POPs-PPh3&S (b) and Rh1/POPs-PPh3 (c) catalysts with the intermediate species of 2 and its corresponding transition state 3 in Fig. 6. C* refers to the carbon in CO, and the C** refers to the carbon in propylene (C3H6).

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Regulating microenvironment of heterogeneous Rh mononuclear complex via sulfur-phosphine co-coordination to enhance the performance of hydroformylation of olefins

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