Citation: Wu Zongfang, Xiong Feng, Wang Zhengming, Huang Weixin. Thermal-, photo-and electron-induced reactivity of hydrogen species on rutile TiO₂(110) surface: Role of oxygen vacancy[J]. Chinese Chemical Letters, ;2018, 29(6): 752-756. doi: 10.1016/j.cclet.2018.01.019 shu

Thermal-, photo-and electron-induced reactivity of hydrogen species on rutile TiO₂(110) surface: Role of oxygen vacancy

Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Materials for Energy Conversion and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China

Corresponding author: Huang Weixin, huangwx@ustc.edu.cn
Received Date: 6 December 2017
Revised Date: 4 January 2018
Accepted Date: 12 January 2018
Available Online: 1 July 2018

Figures(5)

Interaction of hydrogen with TiO₂ plays a vital role in TiO₂-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species on a rutile TiO₂(110) surface formed by atomic H exposure at 320 and 115 K by means of thermal desorption spectroscopy, X-ray photoelectron spectroscopy and low energy electron diffraction. Atomic H interaction with rutile TiO₂(110) at 115 K forms surface Ti—H hydride, surface hydroxyl group, and chemisorbed water. Upon heating, surface Ti—H hydride reacts to produce H₂ while surface hydroxyl groups react to form both water and H₂. Atomic H interaction with rutile TiO₂(110) at 320 K strongly reduces TiO₂ due to the continuous formation and desorption of water and forms surface hydroxyl groups and likely subsurface/bulk hydrogen species. Upon heating, hydrogen forms as the only gas-phase product and its desorption activation energy decreases with the subsurface/bulk reduction extent of rutile TiO₂(110). Surface Ti—H hydride exhibits photo-induced reactivity while both surface Ti—H hydride and surface hydroxyl group exhibit electro-induced reactivity. These results have important implications for understanding the hydrogen-involved thermal and photo reactions on TiO₂-based catalysts.
- Surface chemistry,
- Atomic H,
- Surface Ti hydride,
- Surface hydroxyl group,
- Subsurface/bulk hydrogen species
1. [1]
  A. Fujishima, K. Honda, Nature 238(1972) 37-38. doi: 10.1038/238037a0
2. [2]
  M.A. Henderson, Surf. Sci. Rep. 66(2011) 185-297. doi: 10.1016/j.surfrep.2011.01.001
3. [3]
  X. Chen, L. Liu, P.Y. Yu, S.S. Mao, Science 331(2011) 746-750. doi: 10.1126/science.1200448
4. [4]
  J.T. Yates, Surf. Sci. 603(2009) 1605-1612. doi: 10.1016/j.susc.2008.11.052
5. [5]
  D.V. Bavykin, J.M. Friedrich, F.C. Walsh, Adv. Mater. 18(2006) 2807-2824. doi: 10.1002/(ISSN)1521-4095
6. [6]
  M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Chem. Rev. 95(1995) 69-96. doi: 10.1021/cr00033a004
7. [7]
  C.L. Pang, R. Lindsay, G. Thornton, Chem. Soc. Rev. 37(2008) 2328-2353. doi: 10.1039/b719085a
8. [8]
  L. B. Mo, Y. Wang, Y. Bai, et al., Sci. Rep. 5(2015) 17634. doi: 10.1038/srep17634
9. [9]
  S. Chen, D. Li, Y. Liu, W. Huang, J. Catal. 341(2016) 126-135. doi: 10.1016/j.jcat.2016.06.016
10. [10]
  Q. Yuan, Z. Wu, Y. Jin, et al., J. Am. Chem. Soc. 135(2013) 5212-5219. doi: 10.1021/ja400978r
11. [11]
  X.L. Yin, M. Calatayud, H. Qiu, et al., ChemPhysChem 9(2008) 253-256. doi: 10.1002/(ISSN)1439-7641
12. [12]
  G.H. Enevoldsen, H.P. Pinto, A.S. Foster, et al., Phys. Rev. Lett.102(2009) 136103. doi: 10.1103/PhysRevLett.102.136103
13. [13]
  Z. Wu, W. Zhang, F. Xiong, et al., Phys. Chem. Chem. Phys.16(2014) 7051-7057. doi: 10.1039/c4cp00697f
14. [14]
  B. Chen, Y. Ma, L. Ding, et al., J. Phys. Chem. C 117(2013) 5800-5810. doi: 10.1021/jp312406f
15. [15]
  L. Xu, W. Zhang, Y. Zhang, et al., J. Phys. Chem. C 115(2011) 6815-6824. doi: 10.1021/jp200423j
16. [16]
  L. Xu, Y. Ma, Y. Zhang, Z. Jiang, W. Huang, J. Am. Chem. Soc. 131(2009) 16366-16367. doi: 10.1021/ja908081s
17. [17]
  W. Huang, W. Ranke, R. Schlögl, J. Phys. Chem. C 111(2007) 2198-2204. doi: 10.1021/jp066584u
18. [18]
  W. Huang, W. Ranke, Surf. Sci. 600(2006) 793-802. doi: 10.1016/j.susc.2005.11.026
19. [19]
  W. Huang, W. Ranke, R. Schlögl, J. Phys. Chem. B 109(2005) 9202-9204. doi: 10.1021/jp0511505
20. [20]
  L. Xu, Z. Wu, Y. Zhang, et al., J. Phys. Chem. C 115(2011) 14290-14299. doi: 10.1021/jp204106u
21. [21]
  Y. Du, N.G. Petrik, N.A. Deskins, et al., Phys. Chem. Chem. Phys.14(2012) 3066-3074. doi: 10.1039/C1CP22515D
22. [22]
  M. Kunat, U. Burghaus, C. Woll, Phys. Chem. Chem. Phys. 6(2004) 4203-4207. doi: 10.1039/B404629C
23. [23]
  J. Leconte, A. Markovits, M.K. Skalli, C. Minot, A. Belmajdoub, Surf. Sci. 497(2002) 194-204. doi: 10.1016/S0039-6028(01)01477-7
24. [24]
  J.M. Pan, B.L. Maschhoff, U. Diebold, T.E. Madey, J. Vac. Sci. Technol. A 10(1992) 2470-2476. doi: 10.1116/1.577986
25. [25]
  S. Suzuki, K. Fukui, H. Onishi, Y. Iwasawa, Phys. Rev. Lett. 84(2000) 2156-2159. doi: 10.1103/PhysRevLett.84.2156
26. [26]
  M.L. Knotek, Surf. Sci. 91(1980) L17-L22.
27. [27]
  Z. Zhang, J.T. Yates, Surf. Sci. 652(2016) 195-199. doi: 10.1016/j.susc.2016.04.015
28. [28]
  R. Wang, H. Fan, Catal. Sci. Technol. 7(2017) 251-264. doi: 10.1039/C6CY02007K
29. [29]
  Z.F. Wu, Y.K. Jin, F. Xiong, G.H. Sun, W.X. Huang, Sci. China Chem. 59(2016) 9.
30. [30]
  J. Tao, Q. Cuan, X.Q. Gong, M. Batzill, J. Phys. Chem. C 116(2012) 20438-20446. doi: 10.1021/jp3064678
31. [31]
  P.A. Redhead, Vacuum 12(1962) 203-211. doi: 10.1016/0042-207X(62)90978-8
1. [1]
  Xin Li , Zhen Xu , Donglei Bu , Jinming Cai , Huamei Chen , Qi Chen , Ting Chen , Fang Cheng , Lifeng Chi , Wenjie Dong , Zhenchao Dong , Shixuan Du , Qitang Fan , Xing Fan , Qiang Fu , Song Gao , Jing Guo , Weijun Guo , Yang He , Shimin Hou , Ying Jiang , Huihui Kong , Baojun Li , Dengyuan Li , Jie Li , Qing Li , Ruoning Li , Shuying Li , Yuxuan Lin , Mengxi Liu , Peinian Liu , Yanyan Liu , Jingtao Lü , Chuanxu Ma , Haoyang Pan , JinLiang Pan , Minghu Pan , Xiaohui Qiu , Ziyong Shen , Shijing Tan , Bing Wang , Dong Wang , Li Wang , Lili Wang , Tao Wang , Xiang Wang , Xingyue Wang , Xueyan Wang , Yansong Wang , Yu Wang , Kai Wu , Wei Xu , Na Xue , Linghao Yan , Fan Yang , Zhiyong Yang , Chi Zhang , Xue Zhang , Yang Zhang , Yao Zhang , Xiong Zhou , Junfa Zhu , Yajie Zhang , Feixue Gao , Yongfeng Wang . Recent progress on surface chemistry Ⅰ: Assembly and reaction. Chinese Chemical Letters, 2024, 35(12): 110055-. doi: 10.1016/j.cclet.2024.110055
2. [2]
  Xin Li , Zhen Xu , Donglei Bu , Jinming Cai , Huamei Chen , Qi Chen , Ting Chen , Fang Cheng , Lifeng Chi , Wenjie Dong , Zhenchao Dong , Shixuan Du , Qitang Fan , Xing Fan , Qiang Fu , Song Gao , Jing Guo , Weijun Guo , Yang He , Shimin Hou , Ying Jiang , Huihui Kong , Baojun Li , Dengyuan Li , Jie Li , Qing Li , Ruoning Li , Shuying Li , Yuxuan Lin , Mengxi Liu , Peinian Liu , Yanyan Liu , Jingtao Lü , Chuanxu Ma , Haoyang Pan , JinLiang Pan , Minghu Pan , Xiaohui Qiu , Ziyong Shen , Qiang Sun , Shijing Tan , Bing Wang , Dong Wang , Li Wang , Lili Wang , Tao Wang , Xiang Wang , Xingyue Wang , Xueyan Wang , Yansong Wang , Yu Wang , Kai Wu , Wei Xu , Na Xue , Linghao Yan , Fan Yang , Zhiyong Yang , Chi Zhang , Xue Zhang , Yang Zhang , Yao Zhang , Xiong Zhou , Junfa Zhu , Yajie Zhang , Feixue Gao , Li Wang . Recent progress on surface chemistry Ⅱ: Property and characterization. Chinese Chemical Letters, 2025, 36(1): 110100-. doi: 10.1016/j.cclet.2024.110100
3. [3]
  Zeyu Jiang , Yadi Wang , Changwei Chen , Chi He . Progress and challenge of functional single-atom catalysts for the catalytic oxidation of volatile organic compounds. Chinese Chemical Letters, 2024, 35(9): 109400-. doi: 10.1016/j.cclet.2023.109400
4. [4]
  Xinxiu Yan , Xizhe Huang , Yangyang Liu , Weishang Jia , Hualin Chen , Qi Yao , Tao Chen . Hyperbranched polyamidoamine protective layer with phosphate and carboxyl groups for dendrite-free Zn metal anodes. Chinese Chemical Letters, 2024, 35(10): 109426-. doi: 10.1016/j.cclet.2023.109426
5. [5]
  Guoliang Liu , Zhiqiang Liu , Anmin Zheng . Modulation of zeolite surface realizes dynamic copper species redispersion. Chinese Journal of Structural Chemistry, 2024, 43(6): 100308-100308. doi: 10.1016/j.cjsc.2024.100308
6. [6]
  Manyu Zhu , Fei Liang , Lie Wu , Zihao Li , Chen Wang , Shule Liu , Xiue Jiang . Revealing the difference of Stark tuning rate between interface and bulk by surface-enhanced infrared absorption spectroscopy. Chinese Chemical Letters, 2025, 36(2): 109962-. doi: 10.1016/j.cclet.2024.109962
7. [7]
  Zhenyu Hu , Zhenchun Yang , Shiqi Zeng , Kun Wang , Lina Li , Chun Hu , Yubao Zhao . Cationic surface polarization centers on ionic carbon nitride for efficient solar-driven H₂O₂ production and pollutant abatement. Chinese Chemical Letters, 2024, 35(10): 109526-. doi: 10.1016/j.cclet.2024.109526
8. [8]
  Zhiwei Zhong , Yanbin Huang , Wantai Yang . A simple photochemical method for surface fluorination using perfluoroketones. Chinese Chemical Letters, 2024, 35(5): 109339-. doi: 10.1016/j.cclet.2023.109339
9. [9]
  Yukai Tong , Zhijun Wu , Bo Zhou , Min Hu , Anpei Ye . Surface tension of single suspended aerosol microdroplets. Chinese Chemical Letters, 2024, 35(4): 109062-. doi: 10.1016/j.cclet.2023.109062
10. [10]
  Yu He , Hao Jiang , Shaoxuan Yuan , Jiayi Lu , Qiang Sun . On-surface photo-induced dechlorination. Chinese Chemical Letters, 2024, 35(9): 109807-. doi: 10.1016/j.cclet.2024.109807
11. [11]
  Zhenchun Yang , Bixiao Guo , Zhenyu Hu , Kun Wang , Jiahao Cui , Lina Li , Chun Hu , Yubao Zhao . Molecular engineering towards dual surface local polarization sites on poly(heptazine imide) framework for boosting H₂O₂ photo-production. Chinese Chemical Letters, 2024, 35(8): 109251-. doi: 10.1016/j.cclet.2023.109251
12. [12]
  Xianxu Chu , Lu Wang , Junru Li , Hui Xu . Surface chemical microenvironment engineering of catalysts by organic molecules for boosting electrocatalytic reaction. Chinese Chemical Letters, 2024, 35(8): 109105-. doi: 10.1016/j.cclet.2023.109105
13. [13]
  Ce Liang , Qiuhui Sun , Adel Al-Salihy , Mengxin Chen , Ping Xu . Recent advances in crystal phase induced surface-enhanced Raman scattering. Chinese Chemical Letters, 2024, 35(9): 109306-. doi: 10.1016/j.cclet.2023.109306
14. [14]
  Wenhao Chen , Jian Du , Hanbin Zhang , Hancheng Wang , Kaicheng Xu , Zhujun Gao , Jiaming Tong , Jin Wang , Junjun Xue , Ting Zhi , Longlu Wang . Surface treatment of GaN nanowires for enhanced photoelectrochemical water-splitting. Chinese Chemical Letters, 2024, 35(9): 109168-. doi: 10.1016/j.cclet.2023.109168
15. [15]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
16. [16]
  Chenghao Ge , Peng Wang , Pei Yuan , Tai Wu , Rongjun Zhao , Rong Huang , Lin Xie , Yong Hua . Tuning hot carrier transfer dynamics by perovskite surface modification. Chinese Chemical Letters, 2024, 35(10): 109352-. doi: 10.1016/j.cclet.2023.109352
17. [17]
  Dongpu Wu , Zheng Yang , Yuchen Xia , Lulu Wu , Yingxia Zhou , Caoyuan Niu , Puhui Xie , Xin Zheng , Zhanqi Cao . Surface controllable wettability using amphiphilic rotaxane molecular shuttles. Chinese Chemical Letters, 2025, 36(2): 110353-. doi: 10.1016/j.cclet.2024.110353
18. [18]
  Lan Ma , Cailu He , Ziqi Liu , Yaohan Yang , Qingxia Ming , Xue Luo , Tianfeng He , Liyun Zhang . Magical Surface Chemistry: Fabrication and Application of Oil-Water Separation Membranes. University Chemistry, 2024, 39(5): 218-227. doi: 10.3866/PKU.DXHX202311046
19. [19]
  Chengde Wang , Liping Huang , Shanshan Wang , Lihao Wu , Yi Wang , Jun Dong . A distinction of gliomas at cellular and tissue level by surface-enhanced Raman scattering spectroscopy. Chinese Chemical Letters, 2024, 35(5): 109383-. doi: 10.1016/j.cclet.2023.109383
20. [20]
  Yujuan Zhao , Zaiwang Zhao . Monolayer mesoporous nanosheets with surface asymmetry via a dual-emulsion-directed monomicelle assembly. Chinese Journal of Structural Chemistry, 2024, 43(2): 100238-100238. doi: 10.1016/j.cjsc.2024.100238

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(704)
HTML views(29)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Thermal-, photo-and electron-induced reactivity of hydrogen species on rutile TiO2(110) surface: Role of oxygen vacancy

Metrics

通讯作者: 陈斌, bchen63@163.com

Thermal-, photo-and electron-induced reactivity of hydrogen species on rutile TiO₂(110) surface: Role of oxygen vacancy