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Title: Inorganic materials for energy conversion
Author: Clark, Joanna Helen
ISNI:       0000 0004 2732 3803
Awarding Body: University of Liverpool
Current Institution: University of Liverpool
Date of Award: 2011
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In an effort to design systems that harvest solar light and convert this into chemical energy, the primary aim of the work presented in this thesis was to develop complex metal oxide materials that were active photocatalysts under visible light. The existing methods for visible light incorporation into photocatalytically active materials are reviewed. Of these, metal to metal charge transfer (MMCT) between bimetallic surface- grafted assemblies was taken as particular inspiration. It was hypothesised that MMCT between metal centres within a bulk complex metal oxide could be similarly applied to yield photocatalytic ally active charge carriers. This approach takes advantage of the stability of bulk systems and the ability to tune the compositions of complex oxide materials. Moreover, it was proposed that MMCT between metal centres located on crystallographically distinct sites of a bulk material would aid charge separation and migration throughout the extended lattice. The optical properties of the RE2 Ti207 (RE = Y, La, Ce, Pr) and Ba2XTizM3015 (X = La, Ce, Pr, Nd, Bi; M = Nb, Ta) series, which include some novel cerium(III) titanates, revealed systematic changes in the electronic structures of these materials. These were rationalised with respect to the energy of Ln 4f states. The proposed electronic structures present the partial achievement of the bulk MMCT hypothesis, with optical transitions from occupied Ce 4f midgap states to the unoccupied primarily Ti 3d conduction band. These Ce3+ /rr" charge transfer materials were inactive photocatalysts, attributed to the presence the Ce 4f-based midgap states that facilitate charge recombination. The double perovskite CaCu3T40IZ, with A-site Cu2+ and B-site Ti4+ cations and whose dielectric properties have been studied extensively in the past, is an ideal candidate for the two site MMCT strategy. Here, the optical and photocatalytic properties, rationalised with the aid of DFT calculations, present the partial achievement of the bulk MMCT hypothesis. Sol-gel derived Pt-CaCu3 Ti4012 is an active photocatalyst toward the visible light photo-oxidation of model pollutants methyl orange (MO) and 4-chlorophenol (4CP). Optical spectra and product analysis show that these reactions proceed via more selective routes than the typical reaction over TiOz P25 under DV light. Interestingly, the products of 4CP photo-oxidation were shown to be dependent on the wavelength of incident light. Cu-doping of BizTiz07 was found to stabilise the pyrochlore structure with respect to the Aurivillius phase Bi4 Ti3012 and to impart significant visible light absorption. Sol-gel derived Pt-BiI.6Cuo.4 Tiz07 photo-oxidised MO under visible light via conventional band gap excitation, as determined by quantum efficiency measurements. In contrast, sol-gel derived Pt-B4 Ti3012 photo-oxidised MO via the excitation of adsorbed MO, and was also active toward 4CP photo-oxidation under visible light. The excitation method, mechanisms and product distributions have been investigated for each of the photo-oxidation reactions presented in this thesis. In particular, the photo- oxidation of MO over some Pt-modified metal oxides has been shown to proceed via excitation of adsorbed MO and not of the semiconductor. Additionally, the mechanism and products of these processes are far more selective than the related DV reactions over TiOz P25, and have been shown to depend to some extent on the semiconductor support.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available