Chinese Journal of Catalysis

Chinese Journal of Catalysis ›› 2026, Vol. 88: 516-527.DOI: 10.1016/S1872-2067(26)65128-5

• Articles • Previous Articles    

Construction of a P/S dual-atom coordinated Co heterogeneous mononuclear complex catalyst for hydroformylation

Sen Fenga,b,1, Cunyao Lib,c,1, Benhan Fanb,c, Guangjun Jib,c, Hong Weia,b, Xinyuan Liub,c, Yang Zhaob,c, Miao Jiangb,c, Li Yanb,c,*(), Qiang Zhoud,*(), Yunjie Dinga,b,e,*()   

  1. a Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, Anhui, China
    b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
    c University of Chinese Academy of Sciences, Beijing 100049, China
    d Ningbo Juhua Chemical & Science Co, Ltd, Ningbo 315000, Zhejiang, China
  • Received:2026-02-20 Accepted:2026-04-13 Online:2026-09-18 Published:2026-09-05
  • About author:First author contact: 共同第一作者.
    Contributed equally to this work.
  • Supported by:
    The National Key R&D Program of China(2023YFA1507500);The National Natural Science Foundation of China(22002152);The National Natural Science Foundation of China(22302192);The Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(GZB20230724);The China Postdoctoral Science Foundation(2024T170900);The China Postdoctoral Science Foundation(2024M763202);The Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1530301);The Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1530303);The Youth Innovation Promotion Association CAS(2023190);The Natural Science Foundation of Liaoning Province-Outstanding Youth Science Foundation(2024JH3/10200014);The Doctoral Research Start-up Fund of Liaoning Province(2024-BSBA-28);The Dalian Outstanding Young Scientificand Technological Talents(2024RY016);The Dalian Institute of Chemical Physics(DICP I202455)

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Abstract:

To replace scarce Rh resources and enhance the recyclability of the metal, we report a novel heterogeneous cobalt mononuclear complex catalyst, which possesses phosphorus-rich polymer backbone and P/S dual-atom coordination sites. This catalyst exhibited a much higher hydroformylation performance of 2,5-DHF compared to the Co-P homogeneous analogue, increasing conversion by 70% and shifting selectivity toward high-value-added 3-Formyl-THF by 15%. Under the optimal reaction conditions, the heterogeneous mononuclear complex Co1/POPs-PPh3-5P&2S catalyst displayed comparable performance of precious Rh-based catalysts, achieving a 96.8% conversion of 2,5-DHF and an 85.6% selectivity of 3-Formyl-THF for at least 5 runs. Comprehensive characterizations (extended X-ray absorption fine structure, X-ray photoelectron spectroscopy, in-situ Fourier transformed infrared, etc.) demonstrated that P/S dual-site coordination regulated the electronic structure of Co active centers. Notably, the incorporation of sulfur increased the difference in adsorption energy barriers between the substrate and its isomerized substrate, thereby promoting the massive generation of 3-Formyl-THF. Besides, time-of-flight secondary ion mass spectrometry and density functional theory calculations successfully evidenced the complete structure of the active center and established a coherent reaction mechanism. This study successfully developed a heterogeneous catalyst system based on a mononuclear cobalt complex，achieving a new strategy for non-noble metal catalysis and providing new insights into energy conservation and efficient resource utilization.

Key words: Dual-site coordination, Heterogeneous mononuclear complex, catalysts, Cobalt catalysts, Porous organic polymers, Heterogeneous hydroformylation of 2,5-dihydrofuran