金红石型TiO<sub>2</sub>(110)表面吸附TiCl<sub>4</sub>的微观机理

doi:10.11896/j.issn.1005-023X.2018.20.006

Abstract
Figure/Table
References
Related Citation (8)

Download:

Full Text ( PDF ) (5607KB)
Export: BibTeX | EndNote (RIS)

Abstract The paper studied the oxygen adsorption of the TiCl₄ molecules in TiO₂(110) on the surface of the bridge by using the density functional theory of plane wave turns potential method, based on which the stable adsorption configurations of adsorption energy, charge density and charge density difference, the density of electronic states, Mulliken charge, and Mulliken population were calculated and analyzed. The research revealed that the TiCl₄ could not be adsorbed in the surface of complete crystal cell while on the surface of the cell with oxygen vacancy, the adsorption of TiCl₄ molecules showed its high downward stability and the adsorption process is exothermic reaction. When the surface oxygen vacancy density were 12.5% and 25%, the surface adsorption energy downward could respectively be -29.780 9 kJ·mol^-1and -48.641 9 kJ·mol^-1, which showed that the higher the density of oxygen vacancy was, the adsorption would be stronger. The band gap reduced from 1.304 eV to 0. 074 eV and 0.015 eV respectively. In addition, the band gap changed narrow which indicated that the higher the density of oxygen vacancy was, the narrower the width of band gap would be. The charge that TiCl₄ molecules transferred to the cell surface was 0.2 eV and 0.26 eV. This results conveyed that with the increase of surface oxygen vacancy density, the charge that TiCl₄ molecules transferred to the cell surface increased, and the oxygen reaction of surface to molecules would be intenser.

Key words： density functional theory nucleus growth oxygen vacancy surface adsorption

Published: 22 November 2018

CLC number:

TF823

	Service
	E-mail this article
	Add to my bookshelf
	Add to citation manager
	E-mail Alert
	RSS
	Articles by authors
	HUANG Jun
	LI Rongxing
	XIE Gang
	TIAN Lin
	YANG Ni
	YU Xiaohua
	LI Wei

Cite this article:

HUANG Jun,LI Rongxing,XIE Gang, et al. Microscopic Mechanism of Rutile Titanium Dioxide (110) Surface Adsorption TiCl₄ Molecule[J]. Materials Reports, 2018, 32(20): 3524-3530.

URL:

http://www.mater-rep.com/EN/10.11896/j.issn.1005-023X.2018.20.006 OR http://www.mater-rep.com/EN/Y2018/V32/I20/3524

1 付一江.2015年钛白粉行业的发展现状及市场走势[C]∥中国涂料、颜料行业工作年会.北京,2016.
2 Maulik M,Yonduck S,Venkatramanan R,et al. Multiscale modeling of TiO₂ nanoparticle production in flame reactors: Effect of chemical mechanism[J]. Industrial & Engineering Chemistry Research,2010,49(21):10663.
3 Shigeharu M,Tsuyoshi Y,Atsuo K,et al. A Mechanism for the production of ultrafine particles of TiO₂ by a gas phase reaction [J]. Powder & Particle,1988,6:65.
4 Sotiris E P,Patrick T S. Competition between gas phase and surface oxidation of TiCl₄ during synthesis of TiO₂ particles[J]. Chemical Engineering Science,1998,53(10):1861.
5 Singh, Ishwar R. Direct numerical simulation and reaction path analysis of titania formation in flame synthesis[C]∥Communication Systems (ICCS),2010 IEEE International Conference on. IEEE,2012:522.
6 Yonduck S, Venkat R, Rodney O F. Large-eddy-simulation-based multiscale modeling of TiO₂ nanoparticle synthesis in a turbulent flame reactor using detailed nucleation chemistry[J]. Chemical Engineering Science,2011,66(19):4370.
7 Ghoshtagore R N. Mechanism of heterogeneous deposition of thin film rutile[J]. Journal of the Electrochemical Society, 1970,117(4):125.
8 Richard H W,Matthew S C,Oliver R I,et al. Toward a comprehensive model of the synthesis of TiO₂ particles from TiCl₄[J]. Industrial & Engineering Chemistry Research,2007,46(19):6147.
9 Richard H W,Raphael A S,Markus K,et al. A detailed kinetic mo-del for combustion synthesis of titania from TiCl₄[J]. Combustion & Flame,2009,156(9):1764.
10 West R H, Beran G J, Green W H, et al. First-principles thermochemistry for the production of TiO₂ from TiCl₄[J]. Journal of Physical Chemistry A,2007,111(18):3560.
11 Shirley R, Akroyd J, Miler L A, et al.Theoretical insights into the surface growth of rutile TiO₂[J]. Combustion & Flame, 2011, 158(10):1868.
12 Cui X,Wang B,Wang Z,et al.Formation and diffusion of oxygen-vacancy pairs on TiO₂(110)-(1×1)[J]. Journal of Chemical Physics,2008,129(4):044703.
13 Wang Zhuo. Theoretical study on surface defects and molecular adsorption of titanium dioxide [D]. Hefei: University of Science and Technology of China,2010(in Chinese).
汪卓.二氧化钛表面缺陷及分子吸附的理论研究[D].合肥:中国科学技术大学,2010.
14 Lin Qiaolu, Li Gongping, Xu Nannan, et al. A first-principles study on magnetic properties of the intrinsic defects in rutile TiO₂[J]. Acta Physica Sinica,2017,66(3):302(in Chinese).
林俏露,李公平,许楠楠,等.金红石TiO₂本征缺陷磁性的第一性原理计算[J].物理学报,2017,66(3):302.
15 Guo Yubao, Yang Ru. Theoretical study on the atomic structure and electronic structure of rutile nano-TiO2(110) surface[J]. Journal of Beijing University of Chemical Technology (Natural Science Edition),2004,31(5):64(in Chinese).
郭玉宝,杨儒.金红石型纳米TiO₂(110)表面原子结构和电子结构的理论研究[J].北京化工大学学报(自然科学版),2004,31(5):64.
16 Inderwildi O R,Kraft M. Adsorption,diffusion and desorption of chlorine on and from rutile TiO₂(110): A theoretical investigation[J]. Chemphyschem,2007,8(3):444.
17 Patrick T S,Olivier C,Stavros T,et al.Titania formation by TiCl₄ gas phase oxidation,surface growth and coagulation[J]. Journal of Aerosol Science,2002,33(1):17.
18 Atsuo K,Katsuki K,Shigeharu M. Growth and transformation of TiO₂ crystallites in aerosol reactor[J]. Aiche Journal,1991,37(3):347.
19 Ulrike D. The surface science of titanium dioxide[J]. Surface Science Reports,2003,48(5-8):53.
20 李健,周勇,译.密度泛函理论[M].北京:国防工业出版社,2014.