a Inner Mongolia Key Laboratory of Green Catalysis, College of Chemistry and Environmental Science, Inner Mongolia Normal University, Hohhot 010022;
b State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, Jilin 130023, China
探求全氟羧酸(Perfluorinated Carboxylic Acids, PFCAs)的降解方法及其降解机理是当前亟待解决的问题. 基于密度泛函理论的Materials Studio (MS)程序包中的CASTEP计算程序, 优化了锐钛矿TiO
2
(101),(001), (110), (210); 金红石TiO
2
(110), (001), (101), (210)和板钛矿TiO
2
(210), (101), (001), (110)晶面的几何结构, 结果发现锐钛矿(101)晶面、金红石(110)晶面和板钛矿(210)晶面的能量最低, 为最稳定的吸附面. 对在最稳定三种TiO
2
吸附面上吸附三氟乙酸(Trifluoroacetic Acid, TFA)的18种吸附方式优化结构的吸附能计算表明, TFA被垂直吸附在板钛矿型TiO
2
(210)表面且羧基端H被Ti原子吸附的吸附方式吸附能最大, 吸附结构最稳定, 为TFA在TiO
2
表面吸附的最佳方式. 分态密度计算表明, 板钛矿(210)面与TFA间存在弱的共价相互作用, 吸附后其表面结构的带隙因TFA中的O和F的2p轨道进入, 带隙由吸附前的3.06 eV降低到吸附后的2.80 eV, 光催化吸收波长由吸附前的385 nm增加到吸附后的443 nm, 提高了可见光的吸收效率.
The method and mechanism on the perfluorinated carboxylic acids (PFCAs) degradation is a hot issue. The crystal lattice structures of the anatase TiO
2
(101), (001), (110), (210), the rutile TiO
2
(110), (001), (101), (210) and the brookite TiO
2
(210), (101), (001), (110) were optimized with the CASTEP program in Materials Studio package based the density functional theory (DFT). It is found that the energies of the anatase (101), rutile (110) and brookite (210) are the lowest, and the most stable adsorption surfaces, respectively. The adsorption energies of the 18 kinds of the optimized modes on the most stable TiO
2
surfaces adsorbed by trifluoroacetic acid (TFA) were calculated. It is indicated that the absorption energy of the mode which the TFA is perpendicular to the brookite (210) surface and the carboxyl group of H adsorbed by Ti atom on the brookite (210) is the biggest, and the adsorption structure is the most stable, and the adsorption mode is the best. The partial state densities for the three kinds of the most stable absorption modes were calculated. It is revealed that the covalent interaction of the TFA on bookite (210) surface is weak, resulted from the narrowing of the band gap that the 2p orbital of O, F of TFA inserts into between the valence band (VB) and conduction band for TiO
2
. In the best adsorption mode, before and after adsorption the band gap goes down from 3.06 eV to 2.80 eV,
i.e.
, photocatalytic wavelength increases from 385 nm to 443 nm, so that the visible light absorption efficiency is increased.
Key words:
CASTEP,
TiO
2
,
trifluoroacetic acid,
adsorption,
density functional theory
崔文颖, 刘子忠, 蒋亚军, 王娜, 封继康. TiO
2
表面吸附三氟乙酸的密度泛函理论研究[J].
化学学报
, 2012, 70(19): 2049-2058.
Cui Wenying, Liu Zizhong, Jiang Yajun, Wang Na, Feng Jikang. Study on Trifluoroacetic Acid Adsorbed on TiO
2
Surface with Density Functional Theory[J]. Acta Chimica Sinica, 2012, 70(19): 2049-2058.
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