上海交通大学学报

上海交通大学学报 >

2025 , Vol. 59 >Issue 7: 1050 - 1058

DOI: https://doi.org/10.16183/j.cnki.jsjtu.2023.456

材料科学与工程

锐钛矿TiO2-x (101)表面硝酸根还原路径的第一性原理计算

  • 贺曦煜 ,
  • 杨帆 ,
  • 章俊良
展开
  • 上海交通大学 机械与动力工程学院,上海 200240
贺曦煜(1999—),硕士生,从事电催化材料的第一性原理研究.
杨 帆,副教授,博士生导师;E-mail:fanyang_0123@sjtu.edu.cn.

收稿日期: 2023-09-11

  修回日期: 2023-10-27

  录用日期: 2023-11-17

  网络出版日期: 2023-12-05

基金资助

国家自然科学基金(52374391)

收起

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

  • HE Xiyu ,
  • YANG Fan ,
  • ZHANG Junliang
Expand
  • School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received date: 2023-09-11

  Revised date: 2023-10-27

  Accepted date: 2023-11-17

  Online published: 2023-12-05

Fold

摘要

为研究硝酸根在锐钛矿TiO2-x(101)表面的还原过程,建立有无氧空位两种表面模型,采用密度泛函理论对硝酸根在两种表面的还原过程进行理论计算,研究氧空位对表面电子结构、硝酸根吸附构型以其吸附能、还原路径、竞争反应和产物选择性的影响.结果表明:氧空位改变硝酸根在表面的吸附构型,显著降低其吸附能,并将电位决定步由硝酸根吸附转变为N原子的氢化过程.此外,氧空位能够大幅提高中间体NO2和NO的脱附能,从而抑制副产物的产生,改善催化剂选择性.氧空位对竞争性析氢反应的促进作用远不及对硝酸根还原反应的促进程度,因此含氧空位的TiO2是电催化硝酸根还原产氨的潜在优异催化剂.

关键词： TiO2; 氧空位; 硝酸根还原; 电催化; 第一性原理计算

本文引用格式

贺曦煜 , 杨帆 , 章俊良 . 锐钛矿TiO2-x (101)表面硝酸根还原路径的第一性原理计算[J]. 上海交通大学学报, 2025 , 59(7) : 1050 -1058 . DOI: 10.16183/j.cnki.jsjtu.2023.456

Abstract

To understand the nitrate reduction process on the (101) surface of anatase TiO2-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 TiO2-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

参考文献

[1] CHEN J G, CROOKS R M, SEEFELDT L C, et al. Beyond fossil fuel-driven nitrogen transformations[J]. Science, 2018, 360(6391): eaar6611.
[2] FU X B, ZHANG J H, KANG Y J. Recent advances and challenges of electrochemical ammonia synthesis[J]. Chem Catalysis, 2022, 2(10): 2590-2613.
[3] WANG Y T, YU Y F, JIA R R, et al. Electrochemical synthesis of nitric acid from air and ammonia through waste utilization[J]. National Science Review, 2019, 6(4): 730-738.
[4] CHEN W D, YANG X Y, CHEN Z D, et al. Emerging applications, developments, prospects, and challenges of electrochemical nitrate-to-ammonia conversion[J]. Advanced Functional Materials, 2023, 33(29): 2300512.
[5] GARCIA-SEGURA S, LANZARINI-LOPES M, HRISTOVSKI K, et al. Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications[J]. Applied Catalysis B: Environmental, 2018, 236: 546-568.
[6] HUANG H, ZHAO M, XING X, et al. In-situ infrared studies of the Cd-UPD mediated reduction of nitrate on gold[J]. Journal of Electroanalytical Chemistry & Interfacial Electrochemistry, 1990, 293(1/2): 279-284.
[7] CHEN J, HE X, ZHAO D L, et al. Greatly enhanced electrochemical nitrate-to-ammonia conversion over an Fe-doped TiO2 nanoribbon array[J]. Green Chemistry, 2022, 24(20): 7913-7917.
[8] WEI Z, NIU X W, YIN H B, et al. Synergistic effect of oxygen defects and hetero-phase junctions of TiO2 for selective nitrate electroreduction to ammonia[J]. Applied Catalysis A: General, 2022, 636: 118596.
[9] JIA R R, WANG Y T, WANG C H, et al. Boosting selective nitrate electroreduction to ammonium by constructing oxygen vacancies in TiO2[J]. ACS Catalysis, 2020, 10(6): 3533-3540.
[10] WANG C, GE X, FAN H Q, et al. Simultaneous tuning of particle size and phase composition of TiO2-δ nanoparticles by a simple liquid immiscibility strategy[J]. Journal of Materials Science & Technology, 2023, 145: 1-6.
[11] ZHANG X, WANG C H, GUO Y M, et al. Cu clusters/TiO2-x with abundant oxygen vacancies for enhanced electrocatalytic nitrate reduction to ammonia[J]. Journal of Materials Chemistry A, 2022, 10(12): 6448-6453.
[12] ZHAO D L, MA C Q, LI J, et al. Direct eight-electron NO3--to-NH3 conversion: Using a Co-doped TiO2 nanoribbon array as a high-efficiency electrocatalyst[J]. Inorganic Chemistry Frontiers, 2022, 9(24): 6412-6417.
[13] TAO H B, FANG L W, CHEN J Z, et al. Identification of surface reactivity descriptor for transition metal oxides in oxygen evolution reaction[J]. Journal of the American Chemical Society, 2016, 138(31): 9978-9985.
[14] ZHANG J B, YIN R G, SHAO Q, et al. Oxygen vacancies in amorphous InOx nanoribbons enhance CO2 adsorption and activation for CO2 electroreduction[J]. Angewandte Chemie International Edition, 2019, 58(17): 5609-5613.
[15] ZENG W, LIU T M, LI T M, et al. First principles study of oxygen adsorption on the anatase TiO2 (101) surface[J]. Physica E: Low-Dimensional Systems & Nanostructures, 2015, 67: 59-64.
[16] KRESSE G, FURTHMüLLER J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[J]. Computational Materials Science, 1996, 6(1): 15-50.
[17] KRESSE G, JOUBERT D. From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Physical Review B, 1999, 59(3): 1758-1775.
[18] BL?CHL P E. Projector augmented-wave method[J]. Physical Review B, 1994, 50(24): 17953-17979.
[19] PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple[J]. Physical Review Letters, 1996, 77(18): 3865-3868.
[20] MATHEW K, SUNDARARAMAN R, LETCHWORTH-WEAVER K, et al. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways[J]. The Journal of Chemical Physics, 2014, 140(8): 084106.
[21] CHASE M W. NIST-JANAF thermochemical tables 2 volume-set, journal of physical and chemical reference data mono-graphs[EB/OL]. (1998-08-01)[2023-07-01]. https://www.nist.gov/publications/nist-janaf-thermochemical-tables-4th-edition.
[22] N?RSKOV J K, ROSSMEISL J, LOGADOTTIR A, et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode[J]. The Journal of Physical Chemistry B, 2004, 108(46): 17886-17892.
[23] WEIRICH T E, WINTERER M, SEIFRIED S, et al. Structure of nanocrystalline anatase solved and refined from electron powder data[J]. Acta Crystallographica Section A Foundations of Crystallography, 2002, 58(4): 308-315.
[24] LIN J S, CHOU W C, LU S Y, et al. Density functional study of the interfacial electron transfer pathway for monolayer-adsorbed InN on the TiO2 anatase (101) surface[J]. The Journal of Physical Chemistry B, 2006, 110(46): 23460-23466.
[25] LIU Q, ZHAN F Q, LUO H, et al. Mechanism of interface engineering for ultrahigh piezo-photoelectric catalytic coupling effect of BaTiO3@TiO2 microflowers[J]. Applied Catalysis B: Environmental, 2022, 318: 121817.
[26] HU T, WANG C H, WANG M T, et al. Theoretical insights into superior nitrate reduction to ammonia performance of copper catalysts[J]. ACS Catalysis, 2021, 11(23): 14417-14427.
Options
文章导航

/

〈 〉