Unveiling active sites and the cooperative role of non-thermal plasma and copper–zinc catalysts in the hydrogenation of CO
            2 to methanol

Shanshan  Xu; Matthew E. Potter; Raquel  Simancas; Lucy Costley-Wood; Boya  Qiu; Xuzhao Liu; Cristina  Stere; María Asunción  Molina; Danial Farooq; Floriana Tuna; Dingyue  Zhang; Shuanglin  Zhang; Huanhao  Chen; Shengzhe  Ding; Xinrui Wang; Sarayute Chansai; Matthew Lindley; Sarah J. Haigh; Armando  Ibraliu; Lan Lan; Piu  Chawdhury; Mariyam  Bi; Otis  Leahair; Yilai  Jiao; Min Hu; Qiang Liu; Toru  Wakihara; Xiaolei Fan; Andrew M. Beale; Christopher Hardacre

doi:10.1038/s41929-025-01477-5

Unveiling active sites and the cooperative role of non-thermal plasma and copper–zinc catalysts in the hydrogenation of CO ₂ to methanol

Shanshan Xu, Matthew E. Potter, Raquel Simancas, Lucy Costley-Wood, Boya Qiu, Xuzhao Liu, Cristina Stere, María Asunción Molina, Danial Farooq, Floriana Tuna, Dingyue Zhang, Shuanglin Zhang, Huanhao Chen, Shengzhe Ding, Xinrui Wang, Sarayute Chansai, Matthew Lindley, Sarah J. Haigh, Armando Ibraliu, Lan LanPiu Chawdhury, Mariyam Bi, Otis Leahair, Yilai Jiao, Min Hu, Qiang Liu, Toru Wakihara, Xiaolei Fan, Andrew M. Beale, Christopher Hardacre

Research output: Contribution to journal › Article › peer-review

Abstract

Methanol synthesis via non-thermal plasma (NTP) catalytic CO ₂ hydrogenation provides a sustainable approach to chemical and fuel production with potential in carbon emissions reduction. However, the underlying mechanisms remain unclear. Here we evaluate the mechanism of NTP-catalytic CO ₂ hydrogenation over Cu–Zn/ZSM-5 through operando X-ray absorption spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy and in situ X-ray pair distribution function. We found that Zn enhances Cu dispersion and reducibility, as well as forming active Cu/ZnO interfacial sites. Beyond the conventional formate pathway on metallic Cu, these interfaces enable an additional CO hydrogenation route, enhancing methanol yield. NTP also promotes gas-phase CO ₂ dissociation to CO, bypassing the reverse water–gas shift step required in thermal catalysis. No Cu/Zn alloy formation was observed, underscoring the importance of metallic Cu and Cu/ZnO interfaces under NTP conditions. Furthermore, NTP stabilizes reduced Cu species, preventing re-oxidation and ensuring sustained catalytic activity. These findings advance the mechanistic understanding of NTP-assisted catalysis. (Figure presented.)

Original language	English
Pages (from-to)	134-147
Number of pages	14
Journal	Nature Catalysis
Volume	9
Issue number	2
Early online date	13 Feb 2026
DOIs	https://doi.org/10.1038/s41929-025-01477-5
Publication status	Published - 28 Feb 2026

Data Availability Statement

The data supporting the results of this study are available within the article and Supplementary Information and via figshare at https://doi.org/10.48420/27161757.v2 (ref. 65). Data are available from the corresponding authors upon request. Source data are provided with this paper.

Funding

This project was funded by the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 101022507 (LAURELIN) and by the Japan Science and Technology Agency under the SICORP programme (grant no. JPMJSC2101). This work was also funded and supported by the Engineering and Physical Sciences Research Council (EPSRC) via the Prosperity Partnership EP/V056565/1 with bp and Johnson Matthey plc in collaboration with Cardiff University and the University of Manchester. H.C. and X.F. thank the National Natural Science Foundation of China (grant nos. W2431016, 22278204), International Science and Technology Cooperation Project of Innovative Supporting Plan from Jiangsu Provincial Department of Science and Technology (grant no. BZ2022040), Wenzhou Basic Research Program (grant nos. G20240011, ZG2024051) and Innovation Fund (grant no. XMGL-KJZX-202204) from the Institute of Wenzhou, Zhejiang University, for supporting the collaboration. We acknowledge the staff of D. Gianolio, L. Keenan at beamline B18 and D. Irving at beamline I15-1 at Diamond for experimental assistance. A.I. was funded through a Facility studentship from the Diamond Light Source, ISIS Neutron and Muon Source and the University of Manchester. This work was carried out with the support of Diamond Light Source, instrument I15-1 (proposal CY33381) for XPDF and B18 (proposal SP32971, SP36241-1) for XAS. TEM access at the University of Manchester was supported by EPSRC grant no. EP/S021531/1 and by the Henry Royce Institute for Advanced Materials, funded through EPSRC grant nos. EP/R00661X/1, EP/S019367/1, EP/P025021/1 and EP/P025498/1. EPR measurements were supported by the National EPR Facility at Manchester, EPSRC grant no. EP/W014521/1.

Funders	Funder number
Cardiff University
Diamond Light Source
Zhejiang University
University of Manchester
Institute of Wenzhou
Engineering and Physical Sciences Research Council	EP/V056565/1
Jiangsu Provincial Department of Science and Technology	BZ2022040
National Key Research and Development Program of China	G20240011, ZG2024051
National Natural Science Foundation of China	W2431016, 22278204
Japan Science and Technology Agency	JPMJSC2101
Horizon 2020 Framework Programme	101022507
ISIS Neutron and Muon Source	EP/S021531/1, CY33381, SP32971, SP36241-1
Henry Royce Institute	EP/S019367/1, EP/W014521/1, EP/R00661X/1, EP/P025021/1, EP/P025498/1
Innovationsfonden	XMGL-KJZX-202204

ASJC Scopus subject areas

Catalysis
Bioengineering
Biochemistry
Process Chemistry and Technology

Access to Document

10.1038/s41929-025-01477-5Licence: CC BY

Cite this

Xu, S., Potter, M. E., Simancas, R., Costley-Wood, L., Qiu, B., Liu, X., Stere, C., Molina, M. A., Farooq, D., Tuna, F., Zhang, D., Zhang, S., Chen, H., Ding, S., Wang, X., Chansai, S., Lindley, M., Haigh, S. J., Ibraliu, A., ... Hardacre, C. (2026). Unveiling active sites and the cooperative role of non-thermal plasma and copper–zinc catalysts in the hydrogenation of CO ₂ to methanol. Nature Catalysis, 9(2), 134-147. https://doi.org/10.1038/s41929-025-01477-5

Xu, S, Potter, ME, Simancas, R, Costley-Wood, L, Qiu, B, Liu, X, Stere, C, Molina, MA, Farooq, D, Tuna, F, Zhang, D, Zhang, S, Chen, H, Ding, S, Wang, X, Chansai, S, Lindley, M, Haigh, SJ, Ibraliu, A, Lan, L, Chawdhury, P, Bi, M, Leahair, O, Jiao, Y, Hu, M, Liu, Q, Wakihara, T, Fan, X, Beale, AM & Hardacre, C 2026, 'Unveiling active sites and the cooperative role of non-thermal plasma and copper–zinc catalysts in the hydrogenation of CO ₂ to methanol', Nature Catalysis, vol. 9, no. 2, pp. 134-147. https://doi.org/10.1038/s41929-025-01477-5

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abstract = "Methanol synthesis via non-thermal plasma (NTP) catalytic CO 2 hydrogenation provides a sustainable approach to chemical and fuel production with potential in carbon emissions reduction. However, the underlying mechanisms remain unclear. Here we evaluate the mechanism of NTP-catalytic CO 2 hydrogenation over Cu–Zn/ZSM-5 through operando X-ray absorption spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy and in situ X-ray pair distribution function. We found that Zn enhances Cu dispersion and reducibility, as well as forming active Cu/ZnO interfacial sites. Beyond the conventional formate pathway on metallic Cu, these interfaces enable an additional CO hydrogenation route, enhancing methanol yield. NTP also promotes gas-phase CO 2 dissociation to CO, bypassing the reverse water–gas shift step required in thermal catalysis. No Cu/Zn alloy formation was observed, underscoring the importance of metallic Cu and Cu/ZnO interfaces under NTP conditions. Furthermore, NTP stabilizes reduced Cu species, preventing re-oxidation and ensuring sustained catalytic activity. These findings advance the mechanistic understanding of NTP-assisted catalysis. (Figure presented.)",

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AU - Qiu, Boya

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AU - Stere, Cristina

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AU - Tuna, Floriana

AU - Zhang, Dingyue

AU - Zhang, Shuanglin

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AU - Ding, Shengzhe

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AU - Lan, Lan

AU - Chawdhury, Piu

AU - Bi, Mariyam

AU - Leahair, Otis

AU - Jiao, Yilai

AU - Hu, Min

AU - Liu, Qiang

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N2 - Methanol synthesis via non-thermal plasma (NTP) catalytic CO 2 hydrogenation provides a sustainable approach to chemical and fuel production with potential in carbon emissions reduction. However, the underlying mechanisms remain unclear. Here we evaluate the mechanism of NTP-catalytic CO 2 hydrogenation over Cu–Zn/ZSM-5 through operando X-ray absorption spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy and in situ X-ray pair distribution function. We found that Zn enhances Cu dispersion and reducibility, as well as forming active Cu/ZnO interfacial sites. Beyond the conventional formate pathway on metallic Cu, these interfaces enable an additional CO hydrogenation route, enhancing methanol yield. NTP also promotes gas-phase CO 2 dissociation to CO, bypassing the reverse water–gas shift step required in thermal catalysis. No Cu/Zn alloy formation was observed, underscoring the importance of metallic Cu and Cu/ZnO interfaces under NTP conditions. Furthermore, NTP stabilizes reduced Cu species, preventing re-oxidation and ensuring sustained catalytic activity. These findings advance the mechanistic understanding of NTP-assisted catalysis. (Figure presented.)

AB - Methanol synthesis via non-thermal plasma (NTP) catalytic CO 2 hydrogenation provides a sustainable approach to chemical and fuel production with potential in carbon emissions reduction. However, the underlying mechanisms remain unclear. Here we evaluate the mechanism of NTP-catalytic CO 2 hydrogenation over Cu–Zn/ZSM-5 through operando X-ray absorption spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy and in situ X-ray pair distribution function. We found that Zn enhances Cu dispersion and reducibility, as well as forming active Cu/ZnO interfacial sites. Beyond the conventional formate pathway on metallic Cu, these interfaces enable an additional CO hydrogenation route, enhancing methanol yield. NTP also promotes gas-phase CO 2 dissociation to CO, bypassing the reverse water–gas shift step required in thermal catalysis. No Cu/Zn alloy formation was observed, underscoring the importance of metallic Cu and Cu/ZnO interfaces under NTP conditions. Furthermore, NTP stabilizes reduced Cu species, preventing re-oxidation and ensuring sustained catalytic activity. These findings advance the mechanistic understanding of NTP-assisted catalysis. (Figure presented.)

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