2025年2月27日出版的《美国化学会杂志》发表了浙江大学张治国研究团队的最新成果，他们报道了负载ZnO的单原子氧化钌催化剂选择性光催化氧化甲烷制备甲基过氧化氢。

该课题组人员报道了单原子氧化钌掺杂ZnO作为CH₄有氧氧化成CH₃OOH的高选择性光催化剂。在最佳条件下，Ru₁O_x/ZnO上CH₃OOH的生成速率达到321 μmol g_cat^-1 h^-1，在模拟太阳辐照下选择性为90.9%。机理研究表明，通过氧还原选择性生成OOH自由基和防止CH₃OOH二次副反应的能力是Ru₁O_x/ZnO的主要优势，这是CH₃OOH对CH₄具有显著选择性的原因。在低石蜡光催化氧化中，单原子氧化钌/氧化锌催化剂对烷基过氧化氢也表现出显著的化学选择性，为烃类底物的一步氧化制备高附加值过氧化氢提供了一种解决方案。

据介绍，在温和条件下，CH₄光氧化生成高选择性的高附加值化学物质为推动可再生能源对天然气资源的合理利用提供了一条有前景的途径。然而，由于活性氧自由基形成的化学选择性差以及初级产物的连续副反应，直接由CH₄氧化合成过氧化物仍然是一个挑战。

附：英文原文

Title: Selective Photocatalytic Aerobic Oxidation of Methane to Methyl Hydroperoxide by ZnO-Loaded Single-Atomic Ruthenium Oxide Catalyst

Author: Hantao Gong, Li Zhang, Caihao Deng, Mingjie Liu, Xiaolong Liu, Yongkang Huang, Kai Zhou, Peipei He, Jing Li, Yiwen Yang, Liang Wang, Qiwei Yang, Zongbi Bao, Qilong Ren, Ting Tan, Siyu Yao, Zhiguo Zhang

Issue&Volume: February 27, 2025

Abstract: Photooxidation of CH₄ to value-added chemicals with high selectivity offers a promising pathway to drive the rational utilization of natural gas resources with renewable energy under mild conditions. However, owing to the poor chemoselectivity of reactive oxygen radical formation and consecutive side reactions of primary products, the synthesis of peroxide directly from CH₄ oxidation remains challenging. Here, we report single-atom ruthenium oxide-doped ZnO as a highly selective photocatalyst for the aerobic oxidation of CH₄ to CH₃OOH. Under optimal conditions, the CH₃OOH formation rate over Ru₁O_x/ZnO reaches 321 μmol g_cat^–1 h^–1 with a high selectivity of 90.9% under simulated solar irradiation. Mechanistic studies reveal that the selective generation of OOH radicals via oxygen reduction and the ability to prevent secondary side reactions of CH₃OOH are the main advantages of Ru₁O_x/ZnO, accounting for the remarkable selectivity of CH₃OOH from CH₄. The single-atom Ru oxide/ZnO catalyst also exhibits remarkable chemoselectivity to alkyl hydroperoxide in the photocatalytic oxidation of low paraffins, which provides a solution to prepare value-added peroxide from a single-step oxidation of hydrocarbon substrates.

DOI: 10.1021/jacs.4c11685

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c11685