First-Principle Investigation of Reaction Pathways for Nitrate Reduction on (101) Surface of Anatase TiO2

doi:10.16183/j.cnki.jsjtu.2023.456

Abstract

Abstract:

To understand the nitrate reduction process on the (101) surface of anatase TiO_2-_x, two surface models one with oxygen vacancies and one without are established. Density functional theory calculations are then employed to reveal the effects of oxygen vacancy on the surface electronic structure, nitrate adsorption configuration and energy, reduction pathways, competitive reactions, and product selectivity. The results show that oxygen vacanies alter the adsorption configuration and significantly reduce the nitrate adsorption energy on the surface, and shift the potential determining step from nitrate adsorption to the subsequent hydrogenation processes. In addition, oxygen vacancies dramatically increase the desorption energy of intermediates such as NO₂ and NO, thus inhibiting the formation of by-products and improving electrocatalytic selectivity. The promotion of the competitive hydrogen evolution reaction by oxygen vacancies is far less pronounced compared to that of nitrate reduction reaction. Therefore, oxygen deficient TiO_2-_x emerges as a promising catalyst for electro-catalyzing nitrate reduction to produce ammonia.

Key words: TiO₂, oxygen vacancy, nitrate reduction reaction, electrocatalysis, first-principle calculation

CLC Number:

O643.36

HE Xiyu, YANG Fan, ZHANG Junliang. First-Principle Investigation of Reaction Pathways for Nitrate Reduction on (101) Surface of Anatase TiO₂[J]. Journal of Shanghai Jiao Tong University, 2025, 59(7): 1050-1058.

Figures/Tables 10

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References 26

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表面	键长/Å
表面	Ti1—O1’	Ti2—O2’	N—O1’	N—O2’
无氧空位表面TiO₂(101)	2.3280	2.7342	1.2873	1.2614
有氧空位表面TiO_2-_x(101)	2.1789	2.3253	1.3161	1.2742

表面	H吸附能	NO₂脱附能	NO脱附能
无氧空位表面TiO₂(101)	0.60	-0.59	-0.33
有氧空位表面TiO_2-_x(101)	0.48	2.56	2.08

First-Principle Investigation of Reaction Pathways for Nitrate Reduction on (101) Surface of Anatase TiO₂

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