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Published December 1, 2020 | Supplemental Material
Journal Article Open

Defective Titanium Dioxide Nanobamboo Arrays Architecture for Photocatalytic Nitrogen Fixation up to 780 nm

Abstract

Solar-driven nitrogen fixation is a potential solution to satisfying industrial and agricultural demand, but is severely hampered by the difficulties in capturing, activating and cleaving the dinitrogen (N₂). Here, the defect TiO₂ nanobamboo arrays (DTiO₂ NBAs) is designed with an electro-reduction strategy, which, for the first time, successfully converted N₂ to ammonia (NH₃) in the visible and near infrared light range under ambient conditions, without any sacrificial agent or noble-metal co-catalysts. A highly selective NH₃ yield of 48.3 mg m⁻² h⁻¹ (178 μmol g⁻¹ h⁻¹, no N₂H₄ formation) is obtained on the DTiO₂ NBAs haired titanium foil. The apparent quantum efficiency (AQE) was measured to be 0.39% at 365 nm, 0.12% at 405 nm, 0.11% at 450 nm, 0.15% at 532 nm, 0.24% at 650 nm, and 0.07% at 780 nm. It is found that the electro-reduction process creates amorphous surface layer with modest oxygen vacancy (O_(vac)) density so as to greatly enhance light harvesting, charge carrier, photo-thermal effect, as well as nitrogen adsorption and hydrogenation activity. The alternating photo-fixation pathway is also confirmed by density functional theory (DFT) calculations. This novel nanobamboo TiO_x architecture shows a potential as a new artificial nitrogen fixation for environmentally friendly NH₃ production.

Additional Information

© 2020 Elsevier B.V. Received 12 May 2020, Revised 19 June 2020, Accepted 21 June 2020, Available online 28 June 2020. This work was financially supported by the National Natural Science Foundation of China (Grant 21777009), the Bill and Melinda Gates Foundation (BMGF RTTC Grants OPP1111246 and OPP1149755), Beijing Natural Science Foundation (Grant 8182031), and Major Science and Technology Program for Water Pollution Control and Treatment (Grant 2018ZX07109). The authors declare no conflict of interest.

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