Citation: Mue Tang, Qiuwen Tong, Yiming Li, Ruchun Jiang, Li Shi, Fei Shen, Yali Wei, Zixun Liu, Shuyue Liu, Jun Zhang, Guangming Jiang. Effective and selective electrocatalytic nitrate reduction to ammonia on urchin-like and defect-enriched titanium oxide microparticles[J]. Chinese Chemical Letters, ;2023, 34(12): 108410. doi: 10.1016/j.cclet.2023.108410 shu

Effective and selective electrocatalytic nitrate reduction to ammonia on urchin-like and defect-enriched titanium oxide microparticles

Mue Tang ^{a, 1} ,
Qiuwen Tong ^{b, 1} ,
Yiming Li ^b ,
Ruchun Jiang ^a ,
Li Shi ^b ,
Fei Shen ^b ,
Yali Wei ^c ,
Zixun Liu ^b ,
Shuyue Liu ^a ,
Jun Zhang ^{a, *,} ,
Guangming Jiang ^{b, *,}

a.
College of Metallurgy and Materials Engineering, Chongqing Key Laboratory of Nano/Micro Composites and Devices, Chongqing University of Science and Technology, Chongqing 401331, China
b.
Engineering Research Center for Waste Oil Recovery Technology and Equipment, Ministry of Education, Chongqing Technology and Business University, Chongqing 400067, China
c.
Sichuan Academy of Environmental Sciences, Chengdu 610041, China

junzhang@cqust.edu.cn

jiangguangming@zju.edu.cn

Received Date: 1 December 2022
Revised Date: 3 March 2023
Accepted Date: 29 March 2023
Available Online: 31 March 2023

Figures(4)

This work reported a facile approach to surface oxygen vacancy (O_V)-enriched urchin-like TiO₂ microparticles (U-TiO₂), which were highly effective and durable in catalyzing selective nitrate reduction to ammonia (NO₃RR). Specifically, the U-TiO₂ delivered a mass activity of 1.15 min⁻¹ mg_catalyst⁻¹, a low yield of toxic NO₂⁻-N intermediate (≤0.4 mg/L) and an exceptional high NH₃-N selectivity of 98.1% in treating 22.5 mg/L of NO₃⁻-N under a potential of -0.60 V vs. RHE, outperforming most of the reported oxide-based catalysts. When comparing the performance of U-TiO₂ with that of the solid amorphous TiO₂ counterpart (A-TiO₂) that had close particle size but more O_V on surfaces, we identified that the O_V was the reactive sites, but rather than its content, the NO₃RR kinetics were primarily limited by the electron and mass transfer at U-TiO₂/water interfaces. Accordingly, the superior performance of U-TiO₂ to A-TiO₂ could be ascribed to the hierarchical urchin-like structure in U-TiO₂. The in-situ DEMS test revealed that the NO₃RR on U-TiO₂ followed a pathway of ^*NO₃⁻ → ^*NO₂⁻→ ^*NO → ^*N → ^*NH → ^*NH₂ → ^*NH₃. We also demonstrated that the U-TiO₂ could keep its robust performance under a wide NO₃⁻-N concentration range and in the presence of some co-existing ions (such as Ca²⁺, Cl⁻, Mg²⁺). However, the presence of humic acid and CO₃²⁻ in water slowed down the NO₃RR on U-TiO₂. This work provides a more fundamental insight into the O_V-driven NO₃RR process on TiO₂, which should benefit for the development of efficient TiO₂-based catalysts.
- Nitrate pollution,
- TiO₂,
- Electrocatalytic nitrate reduction,
- Oxygen vacancy,
- Ammonia selectivity
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