TiO2-x/CoOx photocatalyst sparkles in photothermocatalytic reduction of CO2 with H2O steam

Li, Yingying; Wang, Changhua; Song, Miao; Li, Dongsheng; Zhang, Xintong; Liu, Yichun

doi:10.1016/j.apcatb.2018.11.022

TiO_2-x/CoO_x photocatalyst sparkles in photothermocatalytic reduction of CO₂ with H₂O steam

Journal Article · Thu Nov 08 00:00:00 EST 2018 · Applied Catalysis. B, Environmental

DOI:https://doi.org/10.1016/j.apcatb.2018.11.022· OSTI ID:1773367

Li, Yingying ^[1]; ^[1]; Song, Miao ^[2]; ^[2]; ^[1]; Liu, Yichun ^[1]

Northeast Normal Univ., Changchun (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Solar photocatalytic production of fuels from CO₂ and H₂O remains a challenging goal. In this paper, we report a strategy to co-modify TiO₂ with oxygen vacancies and CoO_x nanoclusters for enhanced photothermocatalytic reduction of CO₂. The TiO_2-x/CoO_x material exhibits prominently enhanced activity for the yield of CH₄ and CO under ultraviolet irradiation at elevated temperature of 393 K, which is 111.3 and 13.2 times greater yield of CH₄ and CO, respectively than the conventional photocatalytic process at 298 K, and 175.1 and 2.9 times greater yield of CH₄ and CO, respectively than the pristine TiO₂ under the same photothermocatalytic conditions. Control experiments over singly modified TiO₂ and doubly modified TiO₂ by different preparation history, together with HRTEM, EPR and transient photovoltage measurements reveal the synergistic effect of oxygen vacancies and surface-grafted CoO_x on the photothermocatalytic reduction of CO₂ to CH₄, i.e. oxygen vacancies at TiO₂ surface facilitate the adsorption and reduction of CO₂ and the dispersion of CoO_x nanoclusters, whereas surface-grafted CoO_x clusters facilitate the hole trapping and the oxidation of H₂O. Thereby the coexistence of oxygen vacancies and CoO_x nanoclusters at TiO₂ surface promote the separation of photogenerated electrons and holes, and remarkably enhance the eight-electron reduction of CO₂ to CH₄ under photothermocatalytic conditions. This study shows the great potential of photo-thermal synergy on CO₂ reduction and provides a promising means to design photothermocatalysts for solar photocatalytic reduction of CO₂ to fuel.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: China Postdoctoral Science Foundation; Jilin Province; Ministry of Education of the People's Republic of China (MOE); National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1773367

Report Number(s):: PNNL-SA--136140

Journal Information:: Applied Catalysis. B, Environmental, Journal Name: Applied Catalysis. B, Environmental Vol. 243; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
CoOx
Oxygen vacancies
Photothermocatalysis
Solar fuel