First-principles Calculation on Pt- and Au-modified Anatase TiO2(101) Surface

doi:10.15541/jim20150362

Abstract

Abstract:

Structure stability and electronic structures of anatase TiO₂(101) surface modified by noble metal Pt and Au have been investigated using plane-wave ultrasoft pseudopotentials. The results show that the adsorption interaction is weak between noble atoms and anatase TiO₂(101) surface, resulting in a slight effect on its electronic structure. However, under O-rich condition, it is found that Pt and Au atoms are favor of the Ti vacancies. Contrary to Au atom, Pt atom tends to diffuse from surface into bulk. Under Ti-rich condition, Pt and Au atoms are favor of the O vacancies. The calculated electronic structures of possible vacancy defects indicate that the appearance of surface vacancies not only avails to wet anatase TiO₂(101) surfaces, but also enables their atoms to appear 5d impurity energy levels in band gap.

Key words: photocatalysis, titanium dioxide, surface modification, electronic structure

CLC Number:

O485

MA Xin-Guo, YAN Jie, CHEN Zi-Meng, ZHU Lin, XU Guo-Wang, HUANG Chu-Yun, LV Hui. First-principles Calculation on Pt- and Au-modified Anatase TiO₂(101) Surface[J]. Journal of Inorganic Materials, 2016, 31(3): 291-297.

Figures/Tables 5

Fig. 1 The structure model of anatase TiO2(101) surface modified noble metal from side and top view(a) and (b) indicate the adsorption above surface; (c) and (d) indicate the adsorption between surface atoms; (e) and (f) indicate the adsorption at Ti vacancy; (g) and (h) indicate the adsorption at O vacancy. Small black and gray spheres represent the O and Ti atoms, respectively. Big blue spheres represent the noble metal atoms

Table 1 Adsorption energies of noble metal adsorbing above surface or adsorbing between surface atoms (eV)

Metal	Type	1×1	1×2
Pt	a1	3.511	1.858
	a2	3.854	―
	i1	―	1.416
	i2	―	2.323
Au	a1	2.423	1.398
	a2	2.405	―
	i1	―	1.455
	i2	―	2.624

Table 2 The adsorption energies of noble metal adsorbing at Ti or O vacancies in TiO2(101) surface (eV)

Metal	Type	1×1		1×2
Metal	Type	O rich	Ti rich	O rich	Ti rich
Pt	S_Ti1	-0.237	10.064	-0.161	4.990
	S_Ti2	-0.490	9.810	-0.331	4.820
	S_O1	5.548	0.398	2.812	0.237
	S_O2	6.043	0.893	2.950	0.375
Au	S_Ti1	1.248	11.548	0.600	5.751
	S_Ti2	1.956	12.256	0.907	6.057
	S_O1	5.501	0.351	2.793	0.218
	S_O2	6.179	1.029	3.067	0.492

Fig. 2 The relation between the adsorption energies of TiO2(101) surface modified noble metal and the relative chemical potential ∆μO

Fig. 3 The energy band structures and the density of states of TiO2(101) surface modified noble metal, whose shaded parts indicate the density of states of the impurity atoms and the standard dotted lines indicate the Fermi level

References 23

[1]	LINSEBIGLER A L, LU G, YATES J T.Photocatalysis on TiO2 surfaces: principles, mechanisms, and selected results.Chem. Rev., 1995, 95(3): 735-751.
[2]	CHEN X B, SHEN S H, GUO L J, et al. Semiconductor-based photocatalytic hydrogen generation. Chem. Rev., 2010, 110(11): 6503-6570.
[3]	DIEBOLD U.The surface science of titanium dioxide.Surf. Sci. Rep., 2003, 48(5-8): 53-229.
[4]	COQUET R, HOWARD K L, WILLOCK D J.Theory and simulation in heterogeneous gold catalysis.Chem. Soc. Rev., 2008, 37(9): 2046-2076.
[5]	COLEMAN H M, CHIANG K, AMAL R.Effects of Ag and Pt on photocatalytic degradation of endocrine disrupting chemicals in water.Chem. Engin. J., 2005, 113(1): 65-72.
[6]	KOZLOVA E A, VORONTSOV A V.Influence of mesoporous and platinum-modified titanium dioxide preparation methods on photocatalytic activity in liquid and gas phase.Appl. Catal. B: Environ., 2007, 77(1/2): 35-45.
[7]	LI C M, ZHANG S T, ZHANG B S, et al. Photohole-oxidation- assisted anchoring of ultra-small Ru clusters onto TiO2 with excellent catalytic activity and stability. J. Mater. Chem. A, 2013, 1(7): 2461-2467.
[8]	METE E, UNER D, GÜLSEREN O, et al. Pt-incorporated anatase TiO2(001) surface for solar cell applications: first-principles density functional theory calculations. Phys. Rev. B, 2009, 79(12): 125418-125432.
[9]	METE E, GÜLSEREN O, ELLIALTIOĞLU Ş. Modification of TiO2(001) surface electronic structure by Au impurity investigated with density functional theory.Phys. Rev. B, 2009, 80(3): 035422-035430.
[10]	MÁRQUEZ A M, PLATA J J, ORTEGA Y, et al. Structural defects in W-doped TiO2(101) anatase surface: density functional study. J. Phys. Chem. C, 2011, 115(34): 16970-16976.
[11]	ZHANG M, JIN Z, ZHANG Z, et al. Study of strong interaction between Pt and TiO2 under oxidizing atmosphere. Appl. Surf. Sci., 2005, 250(1-4): 29-34.
[12]	PERKAS N, POL V G, POL S V, et al. Golden-induced crystallization of SiO2 and TiO2 powders. Cryst. Growth Des., 2006, 6: 293-296.
[13]	MA X G, TANG C Q, HUANG J Q, et al. First-principle calculations on the geometry and relaxation structure of anatase TiO2(101) surface. Acta Phys. Sin., 2006, 55(8): 4208-4214.
[14]	MA X G, JIANG J J, LIANG P.Theory study of native point defects on anatase TiO2(101) surface.Acta Phys. Sin., 2008, 57(12): 3120-3125.
[15]	VANDERBILT D.Soft self-consistent pseudopotentials in a generalized eigenvalue formalism.Phys. Rev. B, 1990, 41(11): 7892-7895.
[16]	PERDEW J P.Density-functional approximation for the correlation energy of the inhomogeneous electron gas.Phys. Rev. B, 1986, 33: 8822-8824.
[17]	SEGALL M D, LINDAN P L D, PROBERT M J, et al. First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys.: Condens Matter, 2002, 14(11): 2717-2744.
[18]	VITTADINI A, SELLONI A.Small gold clusters on stoichiometric and defected TiO2 anatase (101) and their interaction with CO: A density functional study.J. Chem. Phys., 2002. 117(1): 353-361.
[19]	WANG Y, HWANG G S.Adsorption of Au atoms on stoichiometric and reduced TiO2(110) rutile surfaces: a first principles study.Surf. Sci., 2003, 542(1/2): 72-80.
[20]	IDDIR H, SKAVYSH V, ÖĞÜT S, et al. Preferential growth of Pt on rutile TiO2. Phys. Rev. B. 2006, 73(4): 041403-041406.
[21]	IDDIR H, ÖĞÜT S, BROWNING N D, et al. Adsorption and diffusion of Pt and Au on the stoichiometric and reduced TiO2 rutile (110) surfaces. Phys. Rev. B, 2005, 72(8): 081407-081410.
[22]	OKAZAKI K, MORIKAWA Y, TANAKA S, et al. Electronic structures of Au on TiO2(110) by first-principles calculations. Phys. Rev. B, 2004, 69(23): 235404-235411.
[23]	MA X G, TANG C Q, YANG X H.Effect of relaxation on the energetics and structure of anatase TiO2(101) surface.Surf. Rev. Lett., 2006, 13(6): 825-831.

First-principles Calculation on Pt- and Au-modified Anatase TiO₂(101) Surface

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 23

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	MA Binbin, ZHONG Wanling, HAN Jian, CHEN Liangyu, SUN Jingjing, LEI Caixia. ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity [J]. Journal of Inorganic Materials, 2024, 39(8): 937-944.
[2]	CAO Qingqing, CHEN Xiangyu, WU Jianhao, WANG Xiaozhuo, WANG Yixuan, WANG Yuhan, LI Chunyan, RU Fei, LI Lan, CHEN Zhi. Visible-light Photodegradation of Tetracycline Hydrochloride on Self-sensitive Carbon-nitride Microspheres Enhanced by SiO₂ [J]. Journal of Inorganic Materials, 2024, 39(7): 787-792.
[3]	CAI Heqing, HAN Lu, YANG Songsong, XUE Xinyu, ZHANG Kou, SUN Zhicheng, LIU Ruping, HU Kun, WEI Yan. Fe₃O₄-DMSA-PEI Magnetic Nanoparticles with Small Particle Size: Preparation and Gene Loading [J]. Journal of Inorganic Materials, 2024, 39(5): 517-524.
[4]	WANG Zhaoyang, QIN Peng, JIANG Yin, FENG Xiaobo, YANG Peizhi, HUANG Fuqiang. Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation [J]. Journal of Inorganic Materials, 2024, 39(4): 383-389.
[5]	WU Lin, HU Minglei, WANG Liping, HUANG Shaomeng, ZHOU Xiangyuan. Preparation of TiHAP@g-C₃N₄ Heterojunction and Photocatalytic Degradation of Methyl Orange [J]. Journal of Inorganic Materials, 2023, 38(5): 503-510.
[6]	LING Jie, ZHOU Anning, WANG Wenzhen, JIA Xinyu, MA Mengdan. Effect of Cu/Mg Ratio on CO₂ Adsorption Performance of Cu/Mg-MOF-74 [J]. Journal of Inorganic Materials, 2023, 38(12): 1379-1386.
[7]	SUN Chen, ZHAO Kunfeng, YI Zhiguo. Research Progress in Catalytic Total Oxidation of Methane [J]. Journal of Inorganic Materials, 2023, 38(11): 1245-1256.
[8]	MA Xinquan, LI Xibao, CHEN Zhi, FENG Zhijun, HUANG Juntong. BiOBr/ZnMoO₄ Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties [J]. Journal of Inorganic Materials, 2023, 38(1): 62-70.
[9]	CHEN Hanxiang, ZHOU Min, MO Zhao, YI Jianjian, LI Huaming, XU Hui. 0D/2D CoN/g-C₃N₄ Composites: Structure and Photocatalytic Performance for Hydrogen Production [J]. Journal of Inorganic Materials, 2022, 37(9): 1001-1008.
[10]	XUE Hongyun, WANG Congyu, MAHMOOD Asad, YU Jiajun, WANG Yan, XIE Xiaofeng, SUN Jing. Two-dimensional g-C₃N₄ Compositing with Ag-TiO₂ as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde [J]. Journal of Inorganic Materials, 2022, 37(8): 865-872.
[11]	WEN Zhiqin, HUANG Binrong, LU Taoyi, ZOU Zhengguang. Pressure on the Structure and Thermal Properties of PbTiO₃: First-principle Study [J]. Journal of Inorganic Materials, 2022, 37(7): 787-794.
[12]	CHI Congcong, QU Panpan, REN Chaonan, XU Xin, BAI Feifei, ZHANG Danjie. Preparation of SiO₂@Ag@SiO₂@TiO₂ Core-shell Structure and Its Photocatalytic Degradation Property [J]. Journal of Inorganic Materials, 2022, 37(7): 750-756.
[13]	WANG Xiaojun, XU Wen, LIU Runlu, PAN Hui, ZHU Shenmin. Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel [J]. Journal of Inorganic Materials, 2022, 37(7): 731-740.
[14]	ZHOU Ganghuai, LIU Yao, SHI Yuan, LIU Shaojun. Slurry Preparation and Stereolithography for Activated Alumina Catalyst Carrier [J]. Journal of Inorganic Materials, 2022, 37(3): 297-302.
[15]	LIU Xuechen, ZENG Di, ZHOU Yuanyi, WANG Haipeng, ZHANG Ling, WANG Wenzhong. Selective Oxidation of Biomass over Modified Carbon Nitride Photocatalysts [J]. Journal of Inorganic Materials, 2022, 37(1): 38-44.