Synergistic effect of Co0 with Cu11In9 intermetallic compound enhancing catalytic performance of CO2 hydrogenation to methanol

doi:10.1016/j.cjche.2025.06.023

Chinese Journal of Chemical Engineering ›› 2025, Vol. 86 ›› Issue (10): 25-33.DOI: 10.1016/j.cjche.2025.06.023

Synergistic effect of Co⁰ with Cu₁₁In₉ intermetallic compound enhancing catalytic performance of CO₂ hydrogenation to methanol

Wei Liu^1,2, Xiaoshen Li^1,2, Shaohui Xiong^1,2, Xueyang Jiang^1,2, Jiayan Yan^1,2, Xiang Duan^1,2, Yingtian Zhang^1,2, Qingpeng Cheng^1,2, Ye Tian^1,2, Xingang Li^1,2

1. State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Haihe Laboratory of Sustainable Chemical Transformations, Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300350, China;
2. Zhejiang Shaoxing Research Institute of Tianjin University, Shaoxing 312300, China

Received:2025-05-08 Revised:2025-06-25 Accepted:2025-06-26 Online:2025-08-12 Published:2025-10-28
Contact: Ye Tian,E-mail:tianye@tju.edu.cn;Xingang Li,E-mail:xingang_li@tju.edu.cn
Supported by:
The authors thank the financial support from the National Key Research and Development Program of China (2022YFB4101800), National Natural Science Foundation of China (22278298) and the Key Research & Development Program of Shandong Province, China (2024CXGC010410).

Synergistic effect of Co⁰ with Cu₁₁In₉ intermetallic compound enhancing catalytic performance of CO₂ hydrogenation to methanol

Wei Liu^1,2, Xiaoshen Li^1,2, Shaohui Xiong^1,2, Xueyang Jiang^1,2, Jiayan Yan^1,2, Xiang Duan^1,2, Yingtian Zhang^1,2, Qingpeng Cheng^1,2, Ye Tian^1,2, Xingang Li^1,2

1. State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Haihe Laboratory of Sustainable Chemical Transformations, Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300350, China;
2. Zhejiang Shaoxing Research Institute of Tianjin University, Shaoxing 312300, China

通讯作者: Ye Tian,E-mail:tianye@tju.edu.cn;Xingang Li,E-mail:xingang_li@tju.edu.cn
基金资助:
The authors thank the financial support from the National Key Research and Development Program of China (2022YFB4101800), National Natural Science Foundation of China (22278298) and the Key Research & Development Program of Shandong Province, China (2024CXGC010410).

Abstract

Abstract: CO₂ hydrogenation to methanol is a critical technology for hydrogen energy conversion and a promising approach to mitigate the energy crisis and greenhouse effect. However, developing highly selective catalysts remains a major challenge for its practical application. Herein, we synthesize an efficient CoCuInO-r catalyst with Cu₁₁In₉ and Co⁰ dual sites on In₂O₃ via a sol-gel method. The Cu₁₁In₉ intermetallic compound enhances H₂ adsorption capacity and strength, and increases oxygen vacancy concentration on the catalyst surface, thereby improving CO₂ activation and hydrogenation efficiency. Meanwhile, Co⁰ suppresses the desorption of the *CO species, facilitating its further hydrogenation to methanol. In-situ DRIFTS experiments indicate that the CO₂ hydrogenation to methanol over CoCuInO-r follows the formate pathway. Compared with CuInO-r (containing Cu₁₁In₉ on In₂O₃), CoCuInO-r exhibits a ～20% increase in methanol selectivity and a 2-fold higher methanol space-time yield, reaching 7.68 mmol·g^-1·h^-1 at 300 °C and 4 MPa.

Key words: Carbon dioxide, Catalyst, Hydrogenation, In₂O₃, Methanol, Intermetallic compound, Dual sites

摘要： CO₂ hydrogenation to methanol is a critical technology for hydrogen energy conversion and a promising approach to mitigate the energy crisis and greenhouse effect. However, developing highly selective catalysts remains a major challenge for its practical application. Herein, we synthesize an efficient CoCuInO-r catalyst with Cu₁₁In₉ and Co⁰ dual sites on In₂O₃ via a sol-gel method. The Cu₁₁In₉ intermetallic compound enhances H₂ adsorption capacity and strength, and increases oxygen vacancy concentration on the catalyst surface, thereby improving CO₂ activation and hydrogenation efficiency. Meanwhile, Co⁰ suppresses the desorption of the *CO species, facilitating its further hydrogenation to methanol. In-situ DRIFTS experiments indicate that the CO₂ hydrogenation to methanol over CoCuInO-r follows the formate pathway. Compared with CuInO-r (containing Cu₁₁In₉ on In₂O₃), CoCuInO-r exhibits a ～20% increase in methanol selectivity and a 2-fold higher methanol space-time yield, reaching 7.68 mmol·g^-1·h^-1 at 300 °C and 4 MPa.

关键词: Carbon dioxide, Catalyst, Hydrogenation, In₂O₃, Methanol, Intermetallic compound, Dual sites

Wei Liu, Xiaoshen Li, Shaohui Xiong, Xueyang Jiang, Jiayan Yan, Xiang Duan, Yingtian Zhang, Qingpeng Cheng, Ye Tian, Xingang Li. Synergistic effect of Co⁰ with Cu₁₁In₉ intermetallic compound enhancing catalytic performance of CO₂ hydrogenation to methanol[J]. Chinese Journal of Chemical Engineering, 2025, 86(10): 25-33.

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Synergistic effect of Co⁰ with Cu₁₁In₉ intermetallic compound enhancing catalytic performance of CO₂ hydrogenation to methanol

Synergistic effect of Co⁰ with Cu₁₁In₉ intermetallic compound enhancing catalytic performance of CO₂ hydrogenation to methanol

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