A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO2 hydrogenation to methanol

Runping Ye; Lixuan Ma; Jianing Mao; Xinyao Wang; Xiaoling Hong; Alessandro Gallo; Yanfu Ma; Wenhao Luo; Baojun Wang; Riguang Zhang; Melis Seher Duyar; Zheng Jiang; Jian Liu

doi:10.1038/s41467-024-46513-3

A Ce-CuZn catalyst with abundant Cu/Zn-O_V-Ce active sites for CO₂ hydrogenation to methanol

Nat Commun. 2024 Mar 9;15(1):2159. doi: 10.1038/s41467-024-46513-3.

Authors

Runping Ye^#¹, Lixuan Ma^#², Jianing Mao^#^{3

4}, Xinyao Wang⁵, Xiaoling Hong⁵, Alessandro Gallo⁶, Yanfu Ma⁵, Wenhao Luo⁷, Baojun Wang², Riguang Zhang⁸, Melis Seher Duyar^{9

10}, Zheng Jiang¹¹, Jian Liu^{12

13

14}

Affiliations

¹ Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, 330031, PR China.
² State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan, 030024, Shanxi, PR China.
³ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, PR China.
⁴ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, PR China.
⁵ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, Liaoning, PR China.
⁶ SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA.
⁷ College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, PR China.
⁸ State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan, 030024, Shanxi, PR China. zhangriguang@tyut.edu.cn.
⁹ DICP-Surrey Joint Centre for Future Materials, and Advanced Technology Institute, University of Surrey, Guilford, Surrey, GU2 7XH, United Kingdom. m.duyar@surrey.ac.uk.
¹⁰ School of Chemistry and Chemical Engineering, University of Surrey, Guildford, Surrey, GU2 7XH, United Kingdom. m.duyar@surrey.ac.uk.
¹¹ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, PR China. jiangz@ustc.edu.cn.
¹² State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, Liaoning, PR China. jian.liu@surrey.ac.uk.
¹³ College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, PR China. jian.liu@surrey.ac.uk.
¹⁴ DICP-Surrey Joint Centre for Future Materials, and Advanced Technology Institute, University of Surrey, Guilford, Surrey, GU2 7XH, United Kingdom. jian.liu@surrey.ac.uk.

^# Contributed equally.

Abstract

CO₂ hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-O_V-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kg_cat^-1·h^-1 with excellent stability for 170 h at 260 °C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO₂ with abundant oxygen vacancies can facilitate H₂ dissociation energetically and thus improve CO₂ hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

Abstract

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