Radiocatalytic Synthesis of Acetic Acid from CH4 and CO2

• Published in: Angewandte Chemie International Edition 2024-10, Vol.63 (44), p.e202407443-n/a
• Main Authors: Mu, Bo‐Shuai, Zhang, Yugang, Peng, Mi, Tu, Zhiyu, Guo, Zhenbo, Shen, Siyong, Xu, Yang, Liang, Weiqiu, Wang, Xianglin, Wang, Meng, Ma, Ding, Liu, Zhibo
• Format: Article
• Language: English
• Subjects: Acetic acid; acetic acid synthesis; Ambient temperature; Anions; Carbon Dioxide; Catalysts; Chemical synthesis; Free radicals; Greenhouse gases; Hydrated electrons; Hydroxyl radicals; Methane; Methyl radicals; Radiation; Radiation absorption; Radiocatalysis; Room temperature; Selectivity; Stability; Titanium dioxide
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202407443

The C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with near‐unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation‐induced chemical conversion. The C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. This study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions (⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with high selectivity (>95 %).