Enabling Specific Photocatalytic Methane Oxidation by Controlling Free Radical Type,Journal of the American Chemical Society

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Enabling Specific Photocatalytic Methane Oxidation by Controlling Free Radical Type
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-17 , DOI: 10.1021/jacs.2c13313
Yuheng Jiang _{1,

2,

3} , Siyang Li _{1,

3,

4} , Shikun Wang _{3,

5} , Yin Zhang ₁ , Chang Long _{1,

6} , Jun Xie _{1,

3} , Xiaoyu Fan ₁ , Wenshi Zhao ₁ , Peng Xu ₇ , Yingying Fan ₈ , Chunhua Cui ₆ , Zhiyong Tang _{1,

3}

Affiliation

Chinese Academy of Science (CAS) Key Laboratory of Nanosystem and Hierarchy Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing100190, P. R. China.
Center for Nanoscale Science and Technology, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing100871, P. R. China.
University of Chinese Academy of Sciences, Beijing100049, P. R. China.
Sino-Danish College, University of Chinese Academy of Sciences, Beijing100049, P. R. China.
State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing100190, P. R. China.
Molecular Electrochemistry Laboratory, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu610054, P. R. China.
CAS Key Laboratory of Standardization and Measurement for Nanotechnology, National Center for Nanoscience and Technology, Beijing100190, P. R. China.
Center for Advanced Analytical Science, School of Chemistry and Chemical Engineering, School of Civil Engineering, Analytical and Testing Center, Guangzhou University, Guangzhou510006, P. R. China.

Selective CH₄ oxidation to CH₃OH or HCHO with O₂ in H₂O under mild conditions provides a desired sustainable pathway for synthesis of commodity chemicals. However, manipulating reaction selectivity while maintaining high productivity remains a huge challenge due to the difficulty in the kinetic control of the formation of a desired oxygenate against its overoxidation. Here, we propose a highly efficient strategy, based on the precise control of the type of as-formed radicals by rational design on photocatalysts, to achieve both high selectivity and high productivity of CH₃OH and HCHO in CH₄ photooxidation for the first time. Through tuning the band structure and the size of active sites (i.e., single atoms or nanoparticles) in our Au/In₂O₃ catalyst, we show alternative formation of two important radicals, ^•OOH and ^•OH, which leads to distinctly different reaction paths to the formation of CH₃OH and HCHO, respectively. This approach gives rise to a remarkable HCHO selectivity and yield of 97.62% and 6.09 mmol g^–1 on In₂O₃-supported Au single atoms (Au₁/In₂O₃) and an exceptional CH₃OH selectivity and yield of 89.42% and 5.95 mmol g^–1 on In₂O₃-supported Au nanoparticles (Au_NPs/In₂O₃), respectively, upon photocatalytic CH₄ oxidation for 3 h at room temperature. This work opens a new avenue toward efficient and selective CH₄ oxidation by delicate design of composite photocatalysts.

中文翻译：

通过控制自由基类型实现特定的光催化甲烷氧化

在温和条件下用 H _{2 O 中的 O}_{2将 CH}₄选择性氧化为 CH ₃ OH 或 HCHO为合成商品化学品提供了所需的可持续途径。然而，由于难以动态控制所需含氧化合物的形成以防止其过氧化，因此在保持高生产率的同时控制反应选择性仍然是一个巨大的挑战。在这里，我们提出了一种高效策略，基于通过合理设计光催化剂精确控制形成的自由基类型，以实现CH _{4中 CH}₃ OH 和 HCHO 的高选择性和高产率第一次光氧化。通过调整我们的 Au/In ₂ O ₃催化剂中的能带结构和活性位点（即单个原子或纳米粒子）的大小，我们展示了两种重要自由基的交替形成，^• OOH 和^• OH，这会导致截然不同的反应分别形成 CH ₃ OH 和 HCHO的途径。这种方法在 In ₂ O ₃负载的 Au 单原子 (Au ₁ /In ₂ O ₃ ) 和特殊的 CH ₃上产生了显着的 HCHO 选择性和 97.62% 和 6.09 mmol g ^{–1的产率}在室温下光催化 CH ₄氧化 3 小时后，在 In ₂ O ₃负载的 Au 纳米粒子 (Au _NPs /In ₂ O ₃ ) 上的 OH 选择性和产率分别为 89.42% 和 5.95 mmol g ^{–1 。}这项工作通过精心设计复合光催化剂，为实现高效和选择性 CH _{4氧化开辟了一条新途径。}

更新日期：2023-01-17

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