Visible Light Photo-oxidation of Model Pollutants Using CaCu3Ti4O12: An Experimental and Theoretical Study of Optical Properties, Electronic Structure, and Selectivity

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• 作者：Joanna H. Clark ; Matthew S. Dyer ; Robert G. Palgrave ; Christopher P. Ireland ; James R. Darwent ; John B. Claridge ; Matthew J. Rosseinsky
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：February 2, 2011
• 年：2011
• 卷：133
• 期：4
• 页码：1016-1032
• 全文大小：1515K
• 年卷期：v.133,no.4(February 2, 2011)
• ISSN：1520-5126

文摘

Charge transfer between metal ions occupying distinct crystallographic sublattices in an ordered material is a strategy to confer visible light absorption on complex oxides to generate potentially catalytically active electron and hole charge carriers. CaCu<sub>3sub>Ti<sub>4sub>O<sub>12sub> has distinct octahedral Ti<sup>4+sup> and square planar Cu<sup>2+sup> sites and is thus a candidate material for this approach. The sol鈭抔el synthesis of high surface area CaCu<sub>3sub>Ti<sub>4sub>O<sub>12sub> and investigation of its optical absorption and photocatalytic reactivity with model pollutants are reported. Two gaps of 2.21 and 1.39 eV are observed in the visible region. These absorptions are explained by LSDA+U electronic structure calculations, including electron correlation on the Cu sites, as arising from transitions from a Cu-hybridized O 2p-derived valence band to localized empty states on Cu (attributed to the isolation of CuO<sub>4sub> units within the structure of CaCu<sub>3sub>Ti<sub>4sub>O<sub>12sub>) and to a Ti-based conduction band. The resulting charge carriers produce selective visible light photodegradation of 4-chlorophenol (monitored by mass spectrometry) by Pt-loaded CaCu<sub>3sub>Ti<sub>4sub>O<sub>12sub> which is attributed to the chemical nature of the photogenerated charge carriers and has a quantum yield comparable with commercial visible light photocatalysts.