Interfacial Behavior of Benzoic Acid and Phenylphosphonic Acid on Nanocrystalline TiO2 Surfaces

被引:16
作者
Ganbold, Erdene-Ochir [1 ]
Lee, Yunhee [2 ]
Lee, Kangtaek [2 ]
Kwon, Ohyun
Joo, Sang-Woo [1 ]
机构
[1] Soongsil Univ, Dept Chem, Seoul 156743, South Korea
[2] Yonsei Univ, Dept Chem Engn, Seoul 120749, South Korea
关键词
carboxylic acids; density functional calculations; IR spectroscopy; phosphonic acids; titanium; SELF-ASSEMBLED MONOLAYERS; SENSITIZED SOLAR-CELLS; FORMIC-ACID; ADSORPTION; RAMAN; SPECTRA; PHOSPHONATE; NANOTUBES; PROPERTY; SILVER;
D O I
10.1002/asia.200900414
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The interfacial behavior of self-assembled thin films of benzoic acid (BA) and phenylphosphonic acid (PPOA) anchored on TiO2 surfaces was studied by using temperature-dependent diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. On the basis of the disappearance of the OH band from the infrared spectra at room temperature, BA and PPOA appear to adsorb onto TiO2 surfaces through carboxylate and phosphonate groups, respectively. Above 420 degrees C, DRIFT spectra indicated that both BA and PPOA desorb from TiO2 surfaces; however, dissimilar desorption behavior could be inferred for BA and PPOA from their temperature-dependent spectral changes. The benzene ring modes of PPOA remained above 420 degrees C, whereas those of BA disappeared. Density functional theory calculations showed that the adsorption of BA and PPOA on TiO2 surfaces corresponded to bidentate bridging geometry on TiO2 surfaces, and the adsorption of PPOA is stronger than that of BA. The monodentate structures with energy differences of 4.9 and 9.1 kcal mol(-1) from the most stable bidentate structures of BA and PPOA, respectively, from the DFT calculations appeared to be possible, particularly at the high temperatures above 420 degrees C, as indicated by the intensified OH bands. The geometry of PPOA was also estimated to be more upright standing than that of BA on TiO2 surfaces, which may lead a rather straight detachment from the TiO2 surfaces based on the presence of in-plane ring modes in the DRIFT spectra at the higher temperature.
引用
收藏
页码:852 / 858
页数:7
相关论文
共 38 条
[1]   Degradation mechanisms in a dye-sensitized solar cell studied by UV-VIS and IR spectroscopy [J].
Agrell, HG ;
Lindgren, J ;
Hagfeldt, A .
SOLAR ENERGY, 2003, 75 (02) :169-180
[2]   Ultrafast electron transfer at the molecule-semiconductor nanoparticle interface [J].
Anderson, NA ;
Lian, TQ .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 2005, 56 :491-519
[3]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[4]   Theoretical modeling of infrared spectra of benzoic acid and its deuterated derivative [J].
Boczar, M ;
Szczeponek, K ;
Wójcik, MJ ;
Paluszkiewicz, C .
JOURNAL OF MOLECULAR STRUCTURE, 2004, 700 (1-3) :39-48
[5]   Density functional theory study of the adsorption of alkanethiols on Cu(111), Ag(111), and Au(111) in the low and high coverage regimes [J].
Cometto, FP ;
Paredes-Olivera, P ;
Macagno, VA ;
Patrito, EM .
JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (46) :21737-21748
[6]   Self-assembled monolayers of α,ω-diphosphonic acids on Ti enable complete or spatially controlled surface derivatization [J].
Danahy, MP ;
Avaltroni, MJ ;
Midwood, KS ;
Schwarzbauer, JE ;
Schwartz, J .
LANGMUIR, 2004, 20 (13) :5333-5337
[7]   Role of molecular anchor groups in molecule-to-semiconductor electron transfer [J].
Ernstorfer, Ralph ;
Gundlach, Lars ;
Felber, Silke ;
Storck, Winfried ;
Eichberger, Rainer ;
Willig, Frank .
JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (50) :25383-25391
[8]   Fluorescence-dip IR spectra of jet-cooled benzoic acid dimer in its ground and first excited singlet states [J].
Florio, GM ;
Sibert, EL ;
Zwier, TS .
FARADAY DISCUSSIONS, 2001, 118 :315-330
[9]  
Frisch M., 2004, GAUSSIAN 03 REVISION, DOI DOI 10.1016/J.MOLSTRUC.2017.03.014
[10]   Self-assembly and bonding of alkanephosphonic acids on the native oxide surface of titanium [J].
Gawalt, ES ;
Avaltroni, MJ ;
Koch, N ;
Schwartz, J .
LANGMUIR, 2001, 17 (19) :5736-5738