Unveiling active sites and the cooperative role of non-thermal plasma and copper–zinc catalysts in the hydrogenation of CO2 to methanol
Methanol synthesis via non-thermal plasma (NTP) catalytic CO<sub>2</sub> 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<sub>2</sub> 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<sub>2</sub> 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.
Authors
- Matthew E. Potter (ORCID: https://orcid.org/0000-0001-9849-3306)
- Xinrui Wang (ORCID: https://orcid.org/0000-0002-8955-0724)
- Cristina Stere (ORCID: https://orcid.org/0000-0001-8604-0211)
- Floriana Tuna (ORCID: https://orcid.org/0000-0002-5541-1750)
- Toru Wakihara (ORCID: https://orcid.org/0000-0002-3916-3849)
- Matthew Lindley (ORCID: https://orcid.org/0000-0002-8164-8479)
- Piu Chawdhury (ORCID: https://orcid.org/0009-0000-5616-5208)
- Boya Qiu (ORCID: https://orcid.org/0000-0002-8644-001X)
- Min Hu (ORCID: https://orcid.org/0000-0002-7563-584X)
- Christopher Hardacre (ORCID: https://orcid.org/0000-0001-7256-6765)
- Danial Farooq (ORCID: https://orcid.org/0000-0002-3004-4528)
- Armando Ibraliu (ORCID: https://orcid.org/0000-0002-5161-2707)
- Dingyue Zhang (ORCID: https://orcid.org/0009-0006-0406-2710)
- Sarah J. Haigh (ORCID: https://orcid.org/0000-0001-5509-6706)
- Raquel Simancas (ORCID: https://orcid.org/0000-0001-7093-2338)
- Lan Lan (ORCID: https://orcid.org/0000-0002-4599-1042)
- Shuanglin Zhang
- Shengzhe Ding (ORCID: https://orcid.org/0000-0003-2822-3882)
- Yilai Jiao
- Lucy Costley-Wood
- Xuzhao Liu
- Xiaolei Fan
- Mariyam Bi
- Sarayute Chansai
- Huanhao Chen
- Otis Leahair
- Shanshan Xu
- M. Asunción Molina
- Qiang Liu
- Andrew M. Beale
Institutions
- Nanjing Tech University (CN)
- Wenzhou University (CN)
- Chinese Academy of Sciences (CN)
- University of Manchester (GB)
- Research Complex at Harwell (GB)
- Designability (GB)
- University College London (GB)
- University of Bath (GB)
- The University of Tokyo (JP)
- Zhejiang University (CN)
Publication Details
- Journal
- Nature Catalysis
- Published
- 2026-02-13
- DOI
- https://doi.org/10.1038/s41929-025-01477-5
- Primary Topic
- Catalysts for Methane Reforming
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Diamond Light Source
- Henry Royce Institute
- European Commission
- Cardiff University
- National Natural Science Foundation of China
- Zhejiang University
- Engineering and Physical Sciences Research Council
- Japan Science and Technology Agency
- Strategic International Collaborative Research Program