膦-硫共配位微环境调控增强Rh单核络合物烯烃多相氢甲酰化活性

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

催化学报 ›› 2025, Vol. 78: 156-169.DOI: 10.1016/S1872-2067(25)64795-4

膦-硫共配位微环境调控增强Rh单核络合物烯烃多相氢甲酰化活性

冯四全^a^,¹, 李存耀^a^,¹, 周宇轩^b^,¹, 宋宪根^a^,^*(), 姜淼^a, 代胡飞^b, 宋尚晟^a, 樊本汉^a, 蔡雨桐^a^,^c, 李彬^a, 袁乔^a^,^c, 李星局^a, 祝雷^a, 张悦^a, 陈维苗^a, 刘涛^a, 严丽^a^,^*(), 龚学庆^d^,^*(), 丁云杰^a^,^e^,^*()

^a中国科学院大连化学物理研究所, 辽宁大连 116023
^b华东理工大学化学与分子工程学院, 上海 200237
^c中国科学院大学, 北京 100049
^d上海交通大学化学化工学院, 上海 200240
^e中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023

收稿日期:2025-05-20 接受日期:2025-07-03 出版日期:2025-11-18 发布日期:2025-10-14
通讯作者: *电子信箱: xiangensong@dicp.ac.cn (宋宪根), yanli@dicp.ac.cn (严丽), xqgong@sjtu.edu.cn (龚学庆), dyj@dicp.ac.cn (丁云杰).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2023YFA1506604);国家重点研发计划(2023YFA1507500);国家自然科学基金(22002156);国家自然科学基金(22002152);国家自然科学基金(22108275);国家自然科学基金(22372161);中科院青促会基金(2022179);中科院青促会基金(2023190);中科院青促会基金(2021181);辽宁省科技攻坚联合项目(3E1731683594447);中国科学院稳定支持基础研究项目(YSBR-022);辽宁省优青项目(2024JH3/10200014);大连市优青项目(2024RY016);大连化物所创新基金(DICP I202117);大连化物所创新基金(DICP I202455)

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.

摘要/Abstract

摘要：

烯烃氢甲酰化是工业上生产重要醛类化学品的关键反应, 具有巨大的工业价值. 铑(Rh)基催化剂因其卓越的催化性能占据核心地位. 然而, 均相Rh催化剂面临催化剂与产物分离困难的问题, 负载型多相催化剂在活性与选择性上常逊色于均相体系, 且其活性中心易受杂质影响而失活. 其中, 硫被广泛认为是贵金属催化剂的强力毒物, 能够显著抑制催化活性与稳定性. 发展兼具高活性、高化学和区域选择性、优异稳定性且能抵抗硫中毒的多相Rh催化剂是本领域的重要挑战. 本文聚焦探索膦与硫的协同配位效应, 旨在通过精确调控单Rh活性位点的配位微环境, 颠覆传统硫中毒认知, 为解决上述挑战提供创新策略.

本文突破性地提出膦-硫(P-S)协同配位调控策略, 设计合成以膦、硫共功能化多孔有机聚合物(POPs-PPh₃&S)为载体的单原子Rh催化剂(Rh₁/POPs-PPh₃&S). 通过精准调控载体中硫与PPh₃的摩尔比例(S/PPh₃), 系统优化了Rh位点的配位微环境, 重点研究了Rh配位微环境对丙烯多相氢甲酰化性能的影响. 结果显示, 当S/PPh₃比例为1:9时, 催化剂性能达到最优. 在丙烯多相氢甲酰化反应中, 转化率达到85.4%, TOF值高达1388 h^-1, 产品选择性98.3%, 是仅含膦配位催化剂Rh₁/POPs-PPh₃ (TOF 925 h^-1)的1.5倍, 正异比从4.6提高到5.6; 同时显著优于仅含硫配位的Rh₁/POPs-S (TOF 598 h^-1, 正异比0.8). 该协同增强效应在高碳数烯烃(1-戊烯、1-己烯、1-庚烯和1-辛烯)的多相氢甲酰化反应中也得到了明确验证. 高温实验结果证实, 适量硫的加入还可以显著降低烯烃异构化和加氢副反应的选择性. 长周期固定床反应(丙烯底物, 稳定运行230 h, 正异比达到9.0左右)证实Rh₁/POPs-PPh₃&S催化剂优异的稳定性: 醛选择性始终维持在约96%的高水平, 且没有失活现象. 综合表征(球差电镜、扩展X射线吸收精细结构、X射线光电子能谱和CO-程序升温脱附)证明了Rh以单原子形式分散, 且形成了独特的P-S协同配位结构. 原位漫反射红外光谱及原位程序升温表面反应-质谱详细揭示了反应物(CO/H₂/丙烯)在催化剂表面的吸附行为、反应中间体演变及产物脱附路径, 阐明了催化循环过程. 密度泛函理论计算深入揭示了P-S协同配位的构效关系与活性提升的微观机制. 膦配位显著提高了Rh中心的电子密度, 而S配位则适度降低了Rh的电子密度, 呈现出了P→Rh→S电荷传输的新机制. P-S协同配位的关键作用在于精细地优化了铑活性中心的最佳电荷状态(即电荷密度). 这种优化显著降低了氢甲酰化决速步——即烯烃插入Rh-H键形成烷基铑中间体这一基元步骤的过渡态能垒, 从而解释了催化活性大幅提升的根本原因.

综上, 本文提出的膦与硫的协同配位打破了烯烃氢甲酰化金属催化剂硫中毒的传统固有认知, 实现了“硫中毒”到“硫促进”的功能转化, 显著提升了Rh单原子催化剂的氢甲酰化活性与稳定性. 本工作不仅为设计高活性、抗硫干扰多相氢甲酰化催化剂提供新范例, 更重要的是首次在原子尺度揭示了硫在特定配位微环境下(协同膦配体)角色由“中毒”到“促进”的根本性转变, 颠覆了贵金属催化剂硫中毒的固有负面认知, 深化了对单原子催化中配位微环境作用机制的理解, 为未来精准设计面向复杂反应环境和实际应用的先进单原子催化剂提供了重要的理论依据和新思路.

关键词: 烯烃多相氢甲酰化, Rh单核络合物催化剂, 硫-膦共配位, 协同作用, 硫中毒, 硫促进, 配位微环境调控

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

冯四全, 李存耀, 周宇轩, 宋宪根, 姜淼, 代胡飞, 宋尚晟, 樊本汉, 蔡雨桐, 李彬, 袁乔, 李星局, 祝雷, 张悦, 陈维苗, 刘涛, 严丽, 龚学庆, 丁云杰. 膦-硫共配位微环境调控增强Rh单核络合物烯烃多相氢甲酰化活性[J]. 催化学报, 2025, 78: 156-169.

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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图/表 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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膦-硫共配位微环境调控增强Rh单核络合物烯烃多相氢甲酰化活性

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

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