Citation: Shuxian He, Fei Shen, Jiahong Zou, Peng Cheng, Wenyang Fu, Yan Zou, Ling Chen, Xiaoshu Lv, Guangming Jiang. Insight into electrocatalytic nitrate reduction to ammonia on titanium oxide: Synergistic effects of crystalline phase and surface oxygen defects[J]. Chinese Chemical Letters, ;2026, 37(3): 111397. doi: 10.1016/j.cclet.2025.111397 shu

Insight into electrocatalytic nitrate reduction to ammonia on titanium oxide: Synergistic effects of crystalline phase and surface oxygen defects

Engineering Research Center for Waste Oil Recovery Technology and Equipment, Ministry of Education, Chongqing Technology and Business University, Chongqing 400067, China

lyuxiaoshu@zju.edu.cn

jiangguangming@zju.edu.cn

Received Date: 17 December 2024
Revised Date: 7 April 2025
Accepted Date: 28 May 2025
Available Online: 29 May 2025

Figures(5)

While TiO₂ is a promising catalyst for electrocatalytic nitrate (NO₃^--N) reduction to NH₃ (ENRR), how the crystalline phase (anatase (A) or rutile (R)) and surface oxygen vacancy (O_v) synergize in ENRR remains ambiguous. Herein a series of nitrogen-doped TiO₂ catalysts with controlled phase composition and O_v number are prepared by calcinating titanium nitride powders in an air atmosphere at specific temperatures (N-TiO₂-x, x = 450–750 ℃). Generally, higher temperatures lead to increased R-TiO₂ content but decreased O_v number. The ENRR performances of these N-TiO₂ are higher than that of pure A- and R-TiO₂, and vary in volcano-like trends against both the R-TiO₂ content and O_v number. Combined control experiments and theoretical simulation demonstrate that O_vs are the active sites for ENRR, but their functions differ between A-TiO₂ and R-TiO₂. Specifically, the O_vs on R-TiO₂ are more active in NO₃^- conversion and renew more easily during reaction, while those on A-TiO₂ perform better in proton adsorption. The synergy between O_vs on R-TiO₂ and A-TiO₂ promotes the ENRR on the phase-mixed N-TiO₂. Furthermore, as the catalyst varies from N-TiO₂–450 to -750, the overall efficacy of O_vs in proton transfer decreases due to the decreased number of O_vs on A-TiO₂, while the mean activity and renewability of them improve as a higher proportion of O_vs are distributed on R-TiO₂. The tug-of-war between the two opposing trends results in a peak ENRR performance on N-TiO₂–650 (mass activity: 22.2 mg_N h^-1 g_cat.^-1; NH₃-N selectivity: 98.8%; Faradaic efficiency: 79.4%). These findings offer a deeper understanding of ENRR on TiO₂, and provide new insights for the design of efficient catalysts.
- Nitrate reduction,
- TiO₂,
- Defects,
- Phase composition,
- Oxygen vacancy
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