PH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films

Chunxing She, Neil A. Anderson, Jianchang Guo, Fang Liu, Wan Hee Goh, Dai Tao Chen, Debra L. Mohler, Zhong Qun Tian, Joseph T Hupp, Tianquan Lian

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Abstract

Photoinduced interfacial electron transfer (ET) from molecular adsorbates to semiconductor nanoparticles has been a subject of intense recent interest. Unlike intramolecular ET, the existence of a quasicontinuum of electronic states in the solid leads to a dependence of ET rate on the density of accepting states in the semiconductor, which varies with the position of the adsorbate excited-state oxidation potential relative to the conduction band edge. For metal oxide semiconductors, their conduction band edge position varies with the pH of the solution, leading to pH-dependent interfacial ET rates in these materials. In this work we examine this dependence in Re(L P)(CO) 3Cl (or ReC1P) [L P = 2,2′-bipyridine-4,4′-bis- CH 2PO(OH) 2] and Re-(L A)(CO) 3Cl (or ReC1A) [L A = 2,2′-bipyridine-4,4′-bis-CH 2COOH] sensitized TiO 2 and ReC1P sensitized SnO 2 nanocrystalline thin films using femtosecond transient IR spectroscopy. ET rates are measured as a function of pH by monitoring the CO stretching modes of the adsorbates and mid-IR absorption of the injected electrons. The injection rate to TiO 2 was found to decrease by 1000-fold from pH 0-9, while it reduced by only a factor of a few to SnO 2 over a similar pH range. Comparison with the theoretical predictions based on Marcus' theory of nonadiabatic interfacial ET suggests that the observed pH-dependent ET rate can be qualitatively accounted for by considering the change of density of electron-accepting states caused by the pH-dependent conduction band edge position.

Original languageEnglish
Pages (from-to)19345-19355
Number of pages11
JournalJournal of Physical Chemistry B
Volume109
Issue number41
DOIs
Publication statusPublished - Oct 20 2005

Fingerprint

2,2'-Dipyridyl
Oxides
metal oxides
electron transfer
Metals
Thin films
Electrons
thin films
Adsorbates
Carbon Monoxide
Conduction bands
conduction bands
methylidyne
Semiconductor materials
Electronic density of states
electron states
metal oxide semiconductors
Electronic states
Excited states
Stretching

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

She, C., Anderson, N. A., Guo, J., Liu, F., Goh, W. H., Chen, D. T., ... Lian, T. (2005). PH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films. Journal of Physical Chemistry B, 109(41), 19345-19355. https://doi.org/10.1021/jp053948u

PH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films. / She, Chunxing; Anderson, Neil A.; Guo, Jianchang; Liu, Fang; Goh, Wan Hee; Chen, Dai Tao; Mohler, Debra L.; Tian, Zhong Qun; Hupp, Joseph T; Lian, Tianquan.

In: Journal of Physical Chemistry B, Vol. 109, No. 41, 20.10.2005, p. 19345-19355.

Research output: Contribution to journalArticle

She, C, Anderson, NA, Guo, J, Liu, F, Goh, WH, Chen, DT, Mohler, DL, Tian, ZQ, Hupp, JT & Lian, T 2005, 'PH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films', Journal of Physical Chemistry B, vol. 109, no. 41, pp. 19345-19355. https://doi.org/10.1021/jp053948u
She, Chunxing ; Anderson, Neil A. ; Guo, Jianchang ; Liu, Fang ; Goh, Wan Hee ; Chen, Dai Tao ; Mohler, Debra L. ; Tian, Zhong Qun ; Hupp, Joseph T ; Lian, Tianquan. / PH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films. In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 41. pp. 19345-19355.
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AU - Liu, Fang

AU - Goh, Wan Hee

AU - Chen, Dai Tao

AU - Mohler, Debra L.

AU - Tian, Zhong Qun

AU - Hupp, Joseph T

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