Edge-rich molybdenum disulfide tailors carbon-chain growth for selective hydrogenation of carbon monoxide to higher alcohols

Jingting Hu; Zeyu Wei; Yunlong Zhang; Rui Huang; Mingchao Zhang; Kang Cheng; Qinghong Zhang; Yutai Qi; Yanan Li; Jun Mao; Junfa Zhu; Lihui Wu; Wu Wen; Shengsheng Yu; Yang Pan; Jiuzhong Yang; Xiangjun Wei; Luozhen Jiang; Rui Si; Liang Yu; Ye Wang; Dehui Deng

doi:10.1038/s41467-023-42325-z

Edge-rich molybdenum disulfide tailors carbon-chain growth for selective hydrogenation of carbon monoxide to higher alcohols

Nat Commun. 2023 Oct 26;14(1):6808. doi: 10.1038/s41467-023-42325-z.

Authors

Jingting Hu^#^{1

2}, Zeyu Wei^#^{1

3}, Yunlong Zhang^{1

3}, Rui Huang¹, Mingchao Zhang², Kang Cheng², Qinghong Zhang², Yutai Qi^{1

2}, Yanan Li^{1

2}, Jun Mao^{1

2}, Junfa Zhu⁴, Lihui Wu⁴, Wu Wen⁴, Shengsheng Yu⁴, Yang Pan⁴, Jiuzhong Yang⁴, Xiangjun Wei⁵, Luozhen Jiang⁶, Rui Si⁶, Liang Yu^{7

8}, Ye Wang⁹, Dehui Deng^{10

11

12}

Affiliations

¹ State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
² State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
³ University of Chinese Academy of Sciences, Beijing, 100049, China.
⁴ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, China.
⁵ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, China.
⁶ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China.
⁷ State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. lyu@dicp.ac.cn.
⁸ University of Chinese Academy of Sciences, Beijing, 100049, China. lyu@dicp.ac.cn.
⁹ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. wangye@xmu.edu.cn.
¹⁰ State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. dhdeng@dicp.ac.cn.
¹¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. dhdeng@dicp.ac.cn.
¹² University of Chinese Academy of Sciences, Beijing, 100049, China. dhdeng@dicp.ac.cn.

^# Contributed equally.

Abstract

Selective hydrogenation of carbon monoxide (CO) to higher alcohols (C₂₊OH) is a promising non-petroleum route for producing high-value chemicals, in which precise regulations of both C-O cleavage and C-C coupling are highly essential but remain great challenges. Herein, we report that highly selective CO hydrogenation to C_2-4OH is achieved over a potassium-modified edge-rich molybdenum disulfide (MoS₂) catalyst, which delivers a high CO conversion of 17% with a superior C_2-4OH selectivity of 45.2% in hydrogenated products at 240 °C and 50 bar, outperforming previously reported non-noble metal-based catalysts under similar conditions. By regulating the relative abundance of edge to basal plane, C_2-4OH to methanol selectivity ratio can be overturned from 0.4 to 2.2. Mechanistic studies reveal that sulfur vacancies at MoS₂ edges boost carbon-chain growth by facilitating not only C-O cleavage but also C-C coupling, while potassium promotes the desorption of alcohols via electrostatic interaction with hydroxyls, thereby enabling preferential formation of C_2-4OH.

Abstract

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