biostudies-literatureSong HState Scholarship Fund by China Scholarship CouncilJSPS KAKENHIPhoto-excitonix Project in Hokkaido UniversityPriority Academic Program Development of Jiangsu Higher Education InstitutionsNational Natural Science Foundation of Chinae202215057https://www.ebi.ac.uk/biostudies/studies/S-EPMC10107830biostudies-literatureUnknown62(4)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.Angewandte Chemie (International ed. in English)Atomically Dispersed Nickel Anchored on a Nitrogen-Doped Carbon/TiO₂ Composite for Efficient and Selective Photocatalytic CH₄ Oxidation to Oxygenates.PMC101078302020083201092212780151872091JP18H02065Feng NJewasuwan WWang QWang SHuang HHu HZhang HSong HMeng XFukata NYe JfalseAtomically Dispersed Nickel Anchored on a Nitrogen-Doped Carbon/TiO₂ Composite for Efficient and Selective Photocatalytic CH₄ Oxidation to Oxygenates.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.2023-01-01T00:00:00Z2023 Jan2025-04-06T11:21:41.233Z2025-04-06T11:21:41.233ZS-EPMC101078303644674010.1002/anie.202215057