Effect of structure on electron transfer reactions between anthracene dyes and TiO2 nanoparticles

被引:93
作者
Martini, I [1 ]
Hodak, JH [1 ]
Hartland, GV [1 ]
机构
[1] Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA
来源
JOURNAL OF PHYSICAL CHEMISTRY B | 1998年 / 102卷 / 47期
关键词
D O I
10.1021/jp982740o
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Photoinduced electron transfer to TiO2 nanoparticles has been examined for the 1-, 2-, and 9-isomers of anthracenecarboxylic acid. TiO2 samples with either anatase or amorphous crystal structures were used for these experiments. The results from time-resolved transient absorption measurements show that the rates of the forward (dye-to-semiconductor) and reverse (semiconductor-to-dye) electron transfer reactions depend on the chemical structure of the dye and the method used to synthesize the particles. These effects arise from differences in both the energetics and the coupling elements for the reactions. Specifically, the reverse electron transfer reactions for the 1- and 2-isomers are significantly faster than that for the 9-isomer due to differences in the oxidation potentials of the dye molecules. In addition, both the forward and reverse electron-transfer times are faster for the anatase TiO2 particles compared to the amorphous particles. For example, the forward electron transfer time for the anatase particles is less than or equal to 200 fs, whereas it is ca. 1.5 ps for the amorphous particles. This is due to a difference in the coupling elements for the forward electron transfer reaction. Finally, all the anthracenecarboxylate dyes examined show red shifts in their W-vis absorption spectra when they are attached to the semiconductor particles. Experiments with ZrO2 show that these shifts are not due to a charge-transfer band. The spectra are more strongly perturbed when the dye molecules are attached to the anatase particles, which shows that for this series of compounds there is a correlation between the spectral shifts and the time scale for electron transfer.
引用
收藏
页码:9508 / 9517
页数:10
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共 52 条
  • [1] [Anonymous], 1977, Quantum mechanics
  • [2] ENHANCED SPECTRAL SENSITIVITY FROM RUTHENIUM(II) POLYPYRIDYL BASED PHOTOVOLTAIC DEVICES
    ARGAZZI, R
    BIGNOZZI, CA
    HEIMER, TA
    CASTELLANO, FN
    MEYER, GJ
    [J]. INORGANIC CHEMISTRY, 1994, 33 (25) : 5741 - 5749
  • [3] Contemporary issues in electron transfer research
    Barbara, PF
    Meyer, TJ
    Ratner, MA
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (31) : 13148 - 13168
  • [4] Measurement of temperature-independent femtosecond interfacial electron transfer from an anchored molecular electron donor to a semiconductor as acceptor
    Burfeindt, B
    Hannappel, T
    Storck, W
    Willig, F
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (41) : 16463 - 16465
  • [5] Ultrafast electron injection: Implications for a photoelectrochemical cell utilizing an anthocyanin dye-sensitized TiO2 nanocrystalline electrode
    Cherepy, NJ
    Smestad, GP
    Gratzel, M
    Zhang, JZ
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (45): : 9342 - 9351
  • [6] FEMTOSECOND STUDY OF THE INTENSITY DEPENDENCE OF ELECTRON-HOLE DYNAMICS IN TIO2 NANOCLUSTERS
    COLOMBO, DP
    ROUSSEL, KA
    SAEH, J
    SKINNER, DE
    CAVALERI, JJ
    BOWMAN, RM
    [J]. CHEMICAL PHYSICS LETTERS, 1995, 232 (03) : 207 - 214
  • [7] Corson D., 1970, ELECTROMAGNETIC FIEL
  • [8] DUONGHONG D, 1982, J AM CHEM SOC, V104, P2977
  • [9] ELECTROCHEMICAL PROPERTIES OF SEMICONDUCTING TIO2 (RUTILE) SINGLE-CRYSTAL ELECTRODE
    DUTOIT, EC
    CARDON, F
    GOMES, WP
    [J]. BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1976, 80 (06): : 475 - 481
  • [10] Dynamics of electron injection in nanocrystalline titanium dioxide films sensitized with [Ru(4,4′-dicarboxy-2,2′-bipyridine)2(NCS)2] by infrared transient absorption
    Ellingson, RJ
    Asbury, JB
    Ferrere, S
    Ghosh, HN
    Sprague, JR
    Lian, TQ
    Nozik, AJ
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 1998, 102 (34): : 6455 - 6458