Atomically Dispersed Nickel Anchored on a Nitrogen-Doped Carbon/TiO2 Composite for Efficient and Selective Photocatalytic CH4 Oxidation to Oxygenates

Hui Song; Hengming Huang; Xianguang Meng; Qi Wang; Huilin Hu; Shengyao Wang; Hongwei Zhang; Wipakorn Jewasuwan; Naoki Fukata; Ningdong Feng; Jinhua Ye

doi:10.1002/anie.202215057

Atomically Dispersed Nickel Anchored on a Nitrogen-Doped Carbon/TiO₂ Composite for Efficient and Selective Photocatalytic CH₄ Oxidation to Oxygenates

Angew Chem Int Ed Engl. 2023 Jan 23;62(4):e202215057. doi: 10.1002/anie.202215057. Epub 2022 Dec 16.

Authors

Hui Song¹, Hengming Huang^{1

2}, Xianguang Meng³, Qi Wang^{1

4}, Huilin Hu⁵, Shengyao Wang⁶, Hongwei Zhang⁷, Wipakorn Jewasuwan¹, Naoki Fukata¹, Ningdong Feng⁸, Jinhua Ye^{1

4

5}

Affiliations

¹ International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan.
² State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009, P. R. China.
³ Hebei Provincial Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan, 063210, P. R. China.
⁴ Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-0814, Japan.
⁵ TJU-NIMS International Collaboration Laboratory, School of Material Science and Engineering, Tianjin University, Tianjin, 300072, P. R. China.
⁶ College of Science, Huazhong Agricultural University, Wuhan, 430070, P. R. China.
⁷ Biogas Institute of Ministry of Agriculture and Rural Affairs, Chengdu, 610041, P. R. China.
⁸ State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, CAS Key Laboratory of Magnetic Resonance in Biological Systems, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, P. R. China.

Abstract

Direct photocatalytic oxidation of methane to liquid oxygenated products is a sustainable strategy for methane valorization at room temperature. However, in this reaction, noble metals are generally needed to function as cocatalysts for obtaining adequate activity and selectivity. Here, we report atomically dispersed nickel anchored on a nitrogen-doped carbon/TiO₂ composite (Ni-NC/TiO₂ ) as a highly active and selective catalyst for photooxidation of CH₄ to C1 oxygenates with O₂ as the only oxidant. Ni-NC/TiO₂ exhibits a yield of C1 oxygenates of 198 μmol for 4 h with a selectivity of 93 %, exceeding that of most reported high-performance photocatalysts. Experimental and theoretical investigations suggest that the single-atom Ni-NC sites not only enhance the transfer of photogenerated electrons from TiO₂ to isolated Ni atoms but also dominantly facilitate the activation of O₂ to form the key intermediate ⋅OOH radicals, which synergistically lead to a substantial enhancement in both activity and selectivity.

Keywords: Oxygenates; Photocatalysis; Selective Methane Oxidation; Single Ni−NC Sites; TiO2.

Abstract

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