Siliceous mesocellular foam supported Cu catalysts for promoting non-thermal plasma activated CO₂ hydrogenation toward methanol synthesis

Abstract

Electrified non-thermal plasma (NTP) catalytic hydrogenation is the promising alternative to the thermal counterparts, being able to be operated under mild conditions and compatible with green electricity/hydrogen. Rational design of the catalysts for such NTP-catalytic systems is one of the keys to improve the process efficiency. Here, we present the development of siliceous mesocellular foam (MCF) supported Cu catalysts for NTP-catalytic CO₂ hydrogenation to methanol. The findings show that the pristine MCF support with high specific surface area and large mesopore of 784 m²·g⁻¹ and ~8.5 nm could promote the plasma discharging and the diffusion of species through its framework, outperforming other control porous materials (viz., silicalite-1, SiO₂, and SBA-15). Compared to the NTP system employing the bare MCF, the inclusion of Cu and Zn in MCF (i.e., Cu₁Zn₁/MCF) promoted the methanol formation of the NTP-catalytic system with a higher space-time yield of methanol at ~275 μmol·g_cat⁻¹·h⁻¹ and a lower energy consumption of 26.4 kJ·{\mathrm{m}\mathrm{m}\mathrm{o}\mathrm{l}}_{{\mathrm{C}\mathrm{H}}_3\mathrm{O}\mathrm{H}}⁻¹ (conversely, ~225 μmol·g_cat⁻¹·h⁻¹ and ~71 kJ·{\mathrm{m}\mathrm{m}\mathrm{o}\mathrm{l}}_{{\mathrm{C}\mathrm{H}}_3\mathrm{O}\mathrm{H}}⁻¹, respectively, for the bare MCF system at 10.1 kV). The findings suggest that inclusion of active metal sites (especially Zn species) could stabilize the CO₂/CO-related intermediates to facilitate the surface reaction toward methanol formation.

Key words： non-thermal plasma (NTP) catalysis; Cu catalyst; CO₂ hydrogenation; methanol; siliceous mesocellular foam (MCF)

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This project has received funding from the International Science and Technology Cooperation Project of Innovative Supporting Plan from Jiangsu Provincial Department of Science and Technology (Grant No. BZ2022040), the National Natural Science Foundation of China (Grant No. 22278204), and the Jiangsu Specially-Appointed Professors Program. This Project was also partially supported by Ningbo Natural Science Foundation (Project ID 2023J245), the special innovation project fund (Grant No. XMGL-KJZX-202204, 52376207, 52276211) from the Institute of Wenzhou, Zhejiang University.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://doi.org/10.1007/s11705-024-2419-z and is accessible for authorized users.

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