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Citation: Hao-Qiang HOU, Li-Fei XU, Zhou XU, Zheng YANG, Wei LI, Chun-Hui MA, Sha LUO, Shou-Xin LIU. Preparation and photocatalytic properties of Cu, N co-doped TiO2 nanotubes for glycerol reforming to syngas[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(11): 2103-2112. doi: 10.11862/CJIC.2023.172 shu

Preparation and photocatalytic properties of Cu, N co-doped TiO2 nanotubes for glycerol reforming to syngas

  • Material Science and Engineering College, Northeast Forestry University, Key Laboratory of Bio-based Material Science & Technology of Ministry of Education, Harbin 150040, China

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  • Cu, N co-doped TiO2 nanotubes (Cu/N-TNT) were prepared by alkaline hydrothermal-ion exchange method, and the photocatalytic properties for glycerol reforming to syngas (H2 and CO) were studied. The results show that Cu/N-TNT catalyst has tubular structures with abundant oxygen vacancies (OV). N forms the impurity energy level by substituting the partial O in the form of Ti-N. Cu is doped into the crystal lattice gap and surface of the catalyst in the form of Cu2+. Cu, N co-doping promotes the effective surface charge separation on the TiO2, and improves the photocatalytic activity and selectivity for glycerol reforming to syngas. CO and H2 yields were 7.3 and 8.5 mmol· g-1 on Cu/N-TNT catalyst doped with 0.15% Cu, which were 9.1 and 70.8 times those on the original TiO2. The molar ratio of H2/CO was increased from 0.52 to 1.18, and the molar ratio of CO/CO2 was raised from 0.21 to 0.42 after 8 h of UV irradiation. N and OV on Cu/N-TNT surface provide the active sites for the decarbonylation of aldehydes and dehydration of formic acid to produce CO. Cu acts as the shallow potential traps to inhibit the electron-hole recombination. Photogenerated holes (h+) play vital roles on the syngas generation during the photocatalytic reforming of glycerol, and excessive hydroxyl radical (·OH) and superoxide radical (·O2-) favor the deep oxidation of glycerol and decrease the selectivity of CO.
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