Shanshan Xu, Matthew E. Potter, Raquel Simancas, Lucy Costley-Wood, Boya Qiu, Xuzhao Liu, Cristina Stere, M. 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
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.