Na驱动的Co2C-Co催化剂用于合成气直接制备长链伯醇

doi:10.1016/S1872-2067(26)64961-3

催化学报

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Na驱动的Co₂C-Co催化剂用于合成气直接制备长链伯醇

李峥^a,c,1, 赵子昂^a,1, 李怡蕙^a, 吕元^a, 严丽^a, 崔文浩^a, 朱顺彬^a,c, 孟宇^d,*, 朱何俊^a,*, 丁云杰^a,b,*

^a中国科学院大连化学物理研究所, 大连洁净能源国家实验室, 辽宁大连 116023;
^b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;
^c中国科学院大学, 北京100049;
^d榆林学院化工学院, 陕西省低变质煤洁净利用重点实验室, 陕西榆林 719000

收稿日期:2025-09-18 接受日期:2025-09-18
通讯作者: *电子信箱: zhuhj@dicp.ac.cn (朱何俊), mengyu@yulinu.edu.cn (孟宇), 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(2023YFB4103100); 中国科学院前瞻战略科技先导专项(XDA29050300); 国家自然科学基金(22002151, 22162028, 22102147); 中国科学技术协会青年人才托举工程(2023QNRC001); 能源催化转化全国重点实验室(2024SKL-B-005); 辽宁滨海实验室(LBLG-2024-06); 陕西省重点研发计划(2022GY-204).

Direct synthesis of long-chain primary alcohols from syngas over Na-driven Co₂C-Co catalyst

Zheng Li^a,c,1, Ziang Zhao^a,1, Yihui Li^a, Yuan Lyu^a, Li Yan^a, Wenhao Cui^a, Shunbin Zhu^a,c, Yu Meng^d,*, Hejun Zhu^a,*, Yunjie Ding^a,b,*

^aDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
^bState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China;
^dShaanxi Key Laboratory of Low Metamorphic Coal Clean Utilization, School of Chemistry and Chemical Engineering, Yulin University, Yulin 719000, Shaanxi, China

Received:2025-09-18 Accepted:2025-09-18
Contact: *E-mail: zhuhj@dicp.ac.cn (H. Zhu), mengyu@yulinu.edu.cn (Y. Meng), dyj@dicp.ac.cn (Y. Ding).
About author:¹ Contributed equally to this work.
Supported by:
National Key Research and Development Program of China (2023YFB4103100), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA29050300), the National Natural Science Foundation of China (22002151, 22162028, 22102147), the Young Elite Scientists Sponsorship Program by CAST (2023QNRC001), the State Key Laboratory of Catalysis (2024SKL-B-005), the Liaoning Binhai Laboratory (LBLG-2024-06, LBLD-2025-08) and the Young Star of Science and Technology in Shaanxi Province (2024ZC-KJXX-088).

摘要/Abstract

摘要： 长链伯醇(C₆₊OH)作为高附加值化学品, 在增塑剂、表面活性剂、香料等精细化工领域具有广泛应用. 从合成气(CO+H₂)出发直接合成长链伯醇是一条具有吸引力的技术路线, 但由于反应过程中CO的解离与非解离吸附并存、碳链增长难以控制, 导致反应网络复杂, 长链伯醇选择性普遍较低. 本文针对上述问题, 通过Na调控Co基催化剂的几何与电子结构, 构建了Na驱动的Co₂C-Co双活性中心, 实现了合成气高选择性制备长链伯醇, 为设计高性能合成气制醇类催化剂提供了新思路.
本研究通过在Co基催化剂中引入Na助剂, 构建了具有Na-Co₂C-Co结构的双活性中心催化剂. 在220 °C, 5.0 MPa, H₂/CO = 2.0和GHSV = 4000 h^‒1的反应条件下, 总醇选择性为45.9%, 其中长链伯醇占比高达65.4%, 是目前文献报道的最优值. 通过对催化剂的物相结构进行系统分析, 发现Na促进了金属Co向Co₂C的原位转化, 形成了稳定的Co₂C-Co复合结构. Na的引入显著改变了催化剂的表面电子性质, 诱导产生了富电子的Co₂C-Co活性位点. Co₂C有利于CO的非解离吸附和插入烃基链, 而金属Co是CO解离吸附和碳链增长的活性位点, 两者的紧密协同作用是提高长链伯醇选择性的重要原因. 化学吸附实验证实了Na能够增强催化剂的表面碱性, 促进碳链增长, 同时显著抑制了H₂的解离与吸附, 形成了相对“富碳贫氢”的表面微环境, 从而抑制了烯烃的深度加氢, 降低烷烃的选择性. 密度泛函理论计算从机理层面揭示了Na-Co₂C-Co位点的作用机制, Na-Co₂C-Co位点显著降低了*C_nH₂_n与*CH₂偶联的能垒(从0.74降至0.10 eV), 促进了碳链增长, 同时降低了*CO插入*C_nH₂_n的能垒(从1.93降至1.20 eV), 并提高了烯烃加氢能垒(从0.13升至1.12 eV), 与实验结果一致, 进一步佐证了Na对于构建Co₂C-Co活性位点和调节表面反应能垒的双重作用.
综上, 本文通过构建Na驱动的Co₂C-Co催化剂, 实现了合成气向长链伯醇的高选择性转化, 揭示了Na在调控活性位点结构与表面反应能垒的关键作用. 该工作为设计高性能Co基催化剂, 推动合成气转化向高值化学品方向发展提供了重要依据.

关键词: 合成气转化, 碱金属, Na驱动的Co₂C-Co催化剂, 长链伯醇, 构效关系

Abstract: The direct synthesis of high-value-added long-chain primary alcohols (LPAs, C₆₊OH) from syngas (CO + H₂) is highly attractive. However, low selectivity of targeted products is generally obtained due to competitive dissociative and non-dissociative CO adsorption, as well as uncontrollable chain growth that causes a complex reaction network. Herein, we report that Na-driven Co₂C-Co dual active sites could be engineered by loading the Na promoter onto an activated carbon supported Co-based catalyst, achieving total alcohol selectivity of ca. 46% with a remarkable LPAs fraction higher than 65%, which represents the first report of high LPA selectivity in literature. Comprehensive characterizations and experiments indicated that electron-rich state of Co₂C-Co sites was generated through Na promotion, which enhances the surface basicity of the catalyst and favors chain propagation. Moreover, Na promotes the dissociation of CO to form *C species, facilitating the transformation of metallic Co into Co₂C and leading to the formation of Na-driven Co₂C-Co active sites that are closely associated with CO insertion. Density functional theory calculations show that Na significantly also promotes C-C coupling while inhibiting hydrogenation and promoting CO insertion, which is deemed to be the intrinsic mechanism behind the high LPAs selectivity. This work elucidates a dual role of Na in constructing active sites and modulating surface reaction energetics, providing a design paradigm to break the LPAs selectivity barrier in syngas conversion.

Key words: Syngas conversion, Alkali metal, Na-driven Co₂C-Co catalyst, Long-chain primary alcohols, Structure-performance relationship

李峥, 赵子昂, 李怡蕙, 吕元, 严丽, 崔文浩, 朱顺彬, 孟宇, 朱何俊, 丁云杰. Na驱动的Co₂C-Co催化剂用于合成气直接制备长链伯醇[J]. 催化学报, DOI: 10.1016/S1872-2067(26)64961-3.

Zheng Li, Ziang Zhao, Yihui Li, Yuan Lyu, Li Yan, Wenhao Cui, Shunbin Zhu, Yu Meng, Hejun Zhu, Yunjie Ding. Direct synthesis of long-chain primary alcohols from syngas over Na-driven Co₂C-Co catalyst[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)64961-3.

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Na驱动的Co₂C-Co催化剂用于合成气直接制备长链伯醇

Direct synthesis of long-chain primary alcohols from syngas over Na-driven Co₂C-Co catalyst

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