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RESEARCH FRONT (Open Access)
Contents Vol 65(6)

Molecular Metal Oxide Cluster-Surface Modified Titanium(iv) Dioxide Photocatalysts

Michael Nolan A C , Anna Iwaszuk A and Hiroaki Tada B C
+ Author Affiliations
- Author Affiliations

A Tyndall National Institute, Lee Maltings, University College Cork, Cork, Ireland.

B Department of Applied Chemistry, School of Science and Engineering, Kinki University, 3-4-1, Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.

C Corresponding authors. Email: h-tada@apch.kindai.ac.jp or michael.nolan@tyndall.ie




Michael Nolan received a BSc in Chemistry with German in 1997 and a Masters and PhD in Microelectronic Engineering from University College Cork in 1999 and 2004. He was a postdoctoral fellow at Trinity College Dublin with Professor Graeme Watson and has been at Tyndall National Institute since 2005, and a staff researcher since 2009.


Anna Iwaszuk was born in Poland. She obtained a BSc in Analytical Chemistry from Hogeschool Zeeland in the Netherlands and MSc in Chemical and Process Engineering from Technical University of Szczecin, Poland. She is currently a PhD student studying metal oxide interfaces with Dr Nolan at the Tyndall National Institute.


Hiroaki Tada received his BS and MS in Engineering from Kyoto University. He received his Dr degree in engineering from Kyoto University in 1991. He joined the research group of Professor A. T. Bell at University of California, Berkeley as an invited scholar in 2002. He is currently a full professor of the School of Science and Engineering at Kinki University.

Australian Journal of Chemistry 65(6) 624-632 https://doi.org/10.1071/CH11451
Submitted: 30 November 2011  Accepted: 30 January 2012   Published: 24 April 2012

Abstract

The surface modification of TiO2 with molecular sized metal oxide clusters has recently been shown to be a promising approach for providing TiO2 with visible-light activity and/or improved UV activity. This short review summarizes the effects of the surface modification of TiO2 with the oxides of iron and tin selected from d- and p-blocks, respectively, on the photocatalytic activity. Fe(acac)3 and [Sn(acac)2]Cl2 chemisorption on the TiO2 surface occurs by ligand-exchange and ion-exchange, respectively. Taking advantage of the strong adsorption, we formed extremely small metal oxide clusters on TiO2 by the chemisorption–calcination cycle (CCC) technique with their loading amount strictly controlled. The iron oxide surface modification of P-25 (anatase/rutile = 4 : 1, w/w, Degussa) gives rise to a high level of visible-light activity and a concomitant increase in the UV-light activity for the degradation of model organic pollutants. On the other hand, only the UV-light activity is increased by the tin oxide surface modification of ST-01 (anatase, Ishihara Sangyo). This striking difference can be rationalized on the basis of the material characterization and DFT calculations, which show that FeOx surface modification of rutile leads to visible-light activity, while SnO2-modified anatase enhances only the UV-light activity. We propose the mechanisms behind the FeOx and SnO2 surface modification, where the surface-to-bulk and bulk-to-surface interfacial electron transfer are taken into account in the former and the latter, respectively.


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