Steering the reaction pathway of methane-to-oxygenates with zero CO2 production via photo–thermal catalysis
- 1State Key Laboratory of Green and Efficient Development of Phosphorus Resources, College of Chemistry, School of Future Technology, Fuzhou University, Fuzhou 350108, China.
Abstract
The direct conversion of CH₄ into liquid oxygenates via heterogeneous catalysis is highly challenging due to the facile overoxidation of target products. Herein, we present a potential Ag-modified In₂O₃ photo-thermal catalyst that enables the selective oxidation of CH₄ to CH₃OH and HCHO using molecular O₂ under mild conditions (150°C, Xe lamp irradiation). The optimized Ag-3/In₂O₃ catalyst exhibits remarkable performance, achieving 100% selectivity toward liquid oxygenates with complete suppression of CO₂ formation, and delivers a high production rate of 6544 μmol · g⁻¹ · h⁻¹, 2.6 times greater than that under pure photocatalysis at 25°C. Mechanistic studies reveal that photogenerated holes facilitate C-H bond activation to form ·CH₃ radicals, while O₂ is selectively reduced at electron-rich Ag sites to generate ·OH species. Meanwhile, it is demonstrated that excessive ·OH generation on the Ag-10/In₂O₃ contrast catalyst promotes HCHO overoxidation to CO₂, highlighting the importance of ·OH regulation in determining product selectivity over the Ag-3/In₂O₃ catalyst. Moreover, combined with experiments and DFT calculations, the results demonstrate that In₂O₃ with a suitable band structure exhibits weak adsorption affinity toward CH₃OH and HCHO, while also providing an in-depth understanding of the zero CO₂ emissions in this catalytic process. The work illustrates that the strategic coupling of thermal and photocatalytic pathways enhances charge-carrier utilization and promotes selective radical chemistry for efficient CH₄ valorization.
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BibTeX
@article{li2026steering,
title = {{Steering the reaction pathway of methane-to-oxygenates with zero CO2 production via photo–thermal catalysis}},
author = {Xia Li and Junzhi Wang and Fengxia Wang and Yajie Fu and Peng Wang and Wei Lin and Yu Tang and Lizhi Wu and Li Tan},
journal = {National science review},
year = {2026},
month = aug,
doi = {10.1093/nsr/nwag472},
url = {https://europepmc.org/article/PMC/PMC13717460},
note = {CC BY},
}
RIS
TY - JOUR
TI - Steering the reaction pathway of methane-to-oxygenates with zero CO2 production via photo–thermal catalysis
AU - Xia Li
AU - Junzhi Wang
AU - Fengxia Wang
AU - Yajie Fu
AU - Peng Wang
AU - Wei Lin
AU - Yu Tang
AU - Lizhi Wu
AU - Li Tan
PY - 2026
DA - 2026/08/05
JO - National science review
DO - 10.1093/nsr/nwag472
UR - https://europepmc.org/article/PMC/PMC13717460
AB - The direct conversion of CH₄ into liquid oxygenates via heterogeneous catalysis is highly challenging due to the facile overoxidation of target products. Herein, we present a potential Ag-modified In₂O₃ photo-thermal catalyst that enables the selective oxidation of CH₄ to CH₃OH and HCHO using molecular O₂ under mild conditions (150°C, Xe lamp irradiation). The optimized Ag-3/In₂O₃ catalyst exhibits remarkable performance, achieving 100% selectivity toward liquid oxygenates with complete suppression of CO₂ formation, and delivers a high production rate of 6544 μmol · g⁻¹ · h⁻¹, 2.6 times greater than that under pure photocatalysis at 25°C. Mechanistic studies reveal that photogenerated holes facilitate C-H bond activation to form ·CH₃ radicals, while O₂ is selectively reduced at electron-rich Ag sites to generate ·OH species. Meanwhile, it is demonstrated that excessive ·OH generation on the Ag-10/In₂O₃ contrast catalyst promotes HCHO overoxidation to CO₂, highlighting the importance of ·OH regulation in determining product selectivity over the Ag-3/In₂O₃ catalyst. Moreover, combined with experiments and DFT calculations, the results demonstrate that In₂O₃ with a suitable band structure exhibits weak adsorption affinity toward CH₃OH and HCHO, while also providing an in-depth understanding of the zero CO₂ emissions in this catalytic process. The work illustrates that the strategic coupling of thermal and photocatalytic pathways enhances charge-carrier utilization and promotes selective radical chemistry for efficient CH₄ valorization.
SN - 2095-5138
SN - 2053-714X
ER -