P/S双原子配位钴基多相单核络合物催化剂的构筑及其氢甲酰化性能的研究

doi:10.1016/S1872-2067(26)65128-5

催化学报 ›› 2026, Vol. 88: 516-527.DOI: 10.1016/S1872-2067(26)65128-5

• 论文 • 上一篇

P/S双原子配位钴基多相单核络合物催化剂的构筑及其氢甲酰化性能的研究

冯森^a^,^b^,¹, 李存耀^b^,^c^,¹, 樊本汉^b^,^c, 姬广军^b^,^c, 韦宏^a^,^b, 刘欣源^b^,^c, 赵阳^b^,^c, 姜淼^b^,^c, 严丽^b^,^c^,^*(), 周强^d^,^*(), 丁云杰^a^,^b^,^e^,^*()

^a 中国科学技术大学化学物理系, 安徽合肥 230026
^b 中国科学院大连化学物理研究所, 辽宁大连 116023
^c 中国科学院大学, 北京 100049
^d 宁波巨化化工科技有限公司, 浙江宁波 315000

收稿日期:2026-02-20 接受日期:2026-04-13 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: yanli@dicp.ac.cn (严丽),
jhzq168@163.com (周强),
dyj@dicp.ac.cn (丁云杰).
基金资助:
国家重点研发计划(2023YFA1507500);国家自然科学基金(22002152);国家自然科学基金(22302192);中国博士后科学基金会(GZB20230724);中国博士后科学基金(2024T170900);中国博士后科学基金(2024M763202);中国科学院战略性先导科技专项(XDB1530301);中国科学院战略性先导科技专项(XDB1530303);中国科学院青年创新促进会(2023190);辽宁省自然科学基金优秀青年科学基金(2024JH3/10200014);辽宁省博士科研启动基金(2024-BSBA-28);大连市杰出青年科技人才项目(2024RY016);大连化学物理研究所自主课题(DICP I202455)

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

Sen Feng^a^,^b^,¹, Cunyao Li^b^,^c^,¹, Benhan Fan^b^,^c, Guangjun Ji^b^,^c, Hong Wei^a^,^b, Xinyuan Liu^b^,^c, Yang Zhao^b^,^c, Miao Jiang^b^,^c, Li Yan^b^,^c^,^*(), Qiang Zhou^d^,^*(), Yunjie Ding^a^,^b^,^e^,^*()

^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:1 共同第一作者.
1 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)

摘要/Abstract

摘要：

氢甲酰化反应是将烯烃转化为高附加值醛类化合物的主要途径, 也是化工领域规模最大的工业过程之一. 其中, 2,5-二氢呋喃(2,5-DHF)作为赤藓糖醇衍生的生物质原料, 通过氢甲酰化反应可以实现3-甲酰基四氢呋喃(3-Formyl-THF)的绿色合成. 3-Formyl-THF及其它呋喃衍生物产品应用广泛、商业价值高, 不仅是药物的重要中间体, 也是农用化学品、高分子工程及超分子表面活性剂等下一代材料的核心组分. 然而, 该反应仍面临两大核心挑战: 一是2,5-DHF在氢甲酰化过程中易异构化为2,3-二氢呋喃, 导致3-Formyl-THF选择性显著降低; 二是目前反应主要依赖铑基均相催化剂, 这类催化剂难以回收, 导致生产成本升高, 阻碍了工业化推广. 因此, 开发廉价、高效且易回收的催化剂, 是3-Formyl-THF合成中亟待解决的难题.
本文通过精准调控载体膦(P)、硫(S)砌块比例, 设计构筑了系列Co₁/POPs-PPh₃-5P&2S双配位多相单核络合物催化剂. 硫的加入既可以调控中心金属Co的电子结构, 又能有效抑制钴活性中心流失, 从而实现可循环的2,5-DHF的高选择性氢甲酰化反应. 优化反应条件后, Co₁/POPs-PPh₃-5P&2S可实现96.8%的2,5-DHF转化率与85.6%的3-Formyl-THF选择性,与铑基贵金属催化剂相媲美, 且可稳定循环至少5次. 相较于传统的Co-P均相催化剂, 该双配位体系使得转化率提升70%, 3-Formyl-THF选择性提高15%. 电镜及固体核磁结果表明, 催化剂中钴以单原子形式高度分散于富磷多孔的聚合物骨架中, 并与P, S原子形成稳定的双位点配位结构. 原位红外、飞行时间二次离子质谱表征结合密度泛函理论计算证明, 钴单核络合物HCo(CO)(PPh₃)₂S为主要活性中心, P/S协同作用不仅显著降低了主反应关键基元步骤的活化能, 同时增大异构化底物与钴活性中心之间的吸附能垒, 在有效抑制副反应路径的同时提高了目标产物的选择性.
综上, 本工作利用P、S双位点间的协同作用, 弥补了单一配位键体系在活性、选择性与稳定性上的不足, 通过电子结构与吸附能的精准调控, 在温和条件下显著提升2,5-DHF氢甲酰化的转化率、选择性与稳定性, 实现了非贵金属对贵金属的替代, 为设计高性能烯烃氢甲酰化多相催化剂提供了新思路.

关键词: 双位点配位, 多相单核络合物催化剂, 钴基催化剂, 多孔有机聚合物, 2,5-二氢呋喃非均相氢甲酰化

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

冯森, 李存耀, 樊本汉, 姬广军, 韦宏, 刘欣源, 赵阳, 姜淼, 严丽, 周强, 丁云杰. P/S双原子配位钴基多相单核络合物催化剂的构筑及其氢甲酰化性能的研究[J]. 催化学报, 2026, 88: 516-527.

Sen Feng, Cunyao Li, Benhan Fan, Guangjun Ji, Hong Wei, Xinyuan Liu, Yang Zhao, Miao Jiang, Li Yan, Qiang Zhou, Yunjie Ding. Construction of a P/S dual-atom coordinated Co heterogeneous mononuclear complex catalyst for hydroformylation[J]. Chinese Journal of Catalysis, 2026, 88: 516-527.

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图/表 7

Scheme 1. Schematic diagram of the reaction pathway of 2.5-DHF.

Fig. 1. (a) Preparation procedure of Co1/POPs-PPh3-5P&2S catalysts. (b,c) Atomic-resolution HAADF-STEM image. STEM image (d,e) and corresponding elemental mapping images (f-i) of Co1/POPs-PPh3-5P&2S catalyst before scanning (d); catalyst after scanning (e).

Fig. 2. (a) The 13C MAS NMR spectra of POPs-PPh3-P&S. (b) The 31P MAS NMR spectra of POPs-PPh3-P&S. (c) The TGA curves of POPs-PPh3-P&S. (d) Comparison of pore volume and specific surface area of POPs-PPh3-P&S s. (e)The nitrogen physical adsorption curves of POPs-PPh3-P&S. (f) The pore distribution curves of POPs-PPh3-P&S.

Fig. 3. XPS Characterization. (a) Co 2p of Co1/POPs-PPh3-P&S. (b) S 2p of POPs-PPh3-5P&2S. (c) S 2p of Co1/POPs-PPh3-5P&2S. (d) Co K-edge Fourier transform spectra of EXAFS. (e) Co K-edge XANES spectra. (f) Co K-edge WT-EXAFS contour plots of different samples. (g) In-situ FT-IR spectra of Co1/POPs-PPh3-5P&2S and Co1/POPs treated under syngas (CO:H2 = 1:1) at 110 °C. (h) In-situ FT-IR spectra of Co1/POPs-PPh3-5P&2S treated with syngas for 30 min and then purged with N2 for 60 min.

Fig. 4. TOF-SIMS of Co1/POPs-PPh3-5P&2S. This experiment was conducted using an ION-TOF GmbH M6. The ion images of various components were obtained on the area of 200 um x 200 um by using a 60 keV Bi3++ primary ion beam.

Fig. 5. (a) Chemical formula for 2,5-DHF hydroformylation (Abbreviations: 3-FT is 3-Formyl-THF; THFA is tetrahydrofurfuryl alcohol; THF is tetrahydrofuran). (b) Evaluation of sample for 2,5-DHF hydroformylation. Standard conditions: S/C = 200, 0.1 g catalyst (Co loading at 2.5%), toluene 5g, 2.5-DHF 0.59 g, 30 h, 120 °C, 6MPa, syngas: CO:H2 = 1:1. (c) Comparison of 2,5-dihydrofuran hydroformylation performance [12,13,17]. The effects of pressure (d), temperature (e), and stability test (f) of Co1/POPs-PPh3-5P&2S in hydroformylation of 2,5-DHF.

Fig. 6. (a) Adsorption energy barrier difference between 2,3-DHF and 2,5-DHF on different catalysts: Co1/POPs-PPh3-5P&2S (top) Co1/POPs-PPh3 (bottom). (b) Proposed catalytic cycle mechanism of HCo(PPh3)2S species in hydroformylation of 2,5-DHF. (c) The energy barrier between the transition states of Co1/POPs-PPh3-5P&2S during the catalytic cycle.

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P/S双原子配位钴基多相单核络合物催化剂的构筑及其氢甲酰化性能的研究

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

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