Now showing 1 - 10 of 11
  • Publication
    Carbon-Doped TiO2 and Carbon, Tungsten-Codoped TiO2 through Sol-Gel Processes in the Presence of Melamine Borate: Reflections through Photocatalysis
    A series of C-doped, W-doped, and C,Wcodoped TiO2 samples have been prepared using modified sol-gel techniques. Reproducible inexpensive C-doping arises from the presence of melamine borate in a sol-gel mixture, whereas W-doping is from the addition of tungstic acid to the sol. The materials have been characterized using elemental analysis, N2 physisorption (BET), thermogravimetric analysis, X-ray diffraction, Raman, X-ray photoelectron, UV-vis spectroscopies, and photocatalytic activity measurements. Doping C and W independently results in an increased absorbance in the visible region of the spectrum with a synergistic effect in increased absorbance when both elements are codoped. The increased visible-light absorbance of the W-doped or codoped materials is not reflected in photocatalytic activity. Visiblelight- induced photocatalytic activity of C-doped material was superior to that of an undoped catalyst, paving the way for its application under only visible-light irradiation conditions. A significant fraction of the spectral red shift commonly observed with doped catalysts might be due to the formation of color centers as a result of defects associated with oxygen vacancies, and bandgap-related narrowing or intragap localization of dopant levels are not the only factors responsible for enhanced visible-light absorption in doped photocatalysts. Furthermore, bandgap narrowing through increases in the energy of the valence band may actually decrease photo-oxidation activity through a curtailment of one route of oxidation.
      849Scopus© Citations 106
  • Publication
    Serendipity following attempts to prepare C-doped rutile TiO2
    Attempts to mimic the band gap narrowing seen in anatase TiO2 following C-doping of the lattice where the C arose from a melamine borate precursor were made in situations where the sol-gel mixture was directed towards rutile formation. The formed materials were characterised using XRD, BET, UV-Vis spectroscopy, XPS and TEM and their activities in promoting the photo-degradation of 4-chlorophenol were analysed. It was found that carbon was not doped into the lattice (in contrast to the situations where the sol-gel mixture was directed towards the precipitation of anatase TiO2). In spite of how common reports of the preparation of C-doped TiO2 using sol-gel processes have been, the presence of carbon dopant precursors in a crystallising sol does not necessarily result in the incorporation of C dopants within the final crystalline material, i.e. the nature of the condensing sol is also important. The presence of melamine borate did however increase the proportion of rutile in the final mixture (indeed in the presence of melamine borate the pure rutile phase was formed) and also resulted in materials with higher surface areas (as measured using BET). Furthermore, TEM has shown that rutile TiO2 condensed in the presence of melamine borate had a much more distinct rod-like shape than that condensed in its absence (the latter being more spherical in shape). These materials, notwithstanding the absence of any dopant effect, demonstrated enhanced photocatalytic activity when compared with analogous materials prepared in the absence of melamine borate and this effect is ascribed to both their relatively larger surface areas and their specific shape. Therefore, we have serendipitously come across a method for improving the performance of rutile photocatalysts while searching for a method to generate C-doped rutile TiO2.
      466Scopus© Citations 11
  • Publication
    Visible Light-Driven Gas-Phase Artificial Photosynthesis Reactions over Ruthenium Metal Nanoparticles Modified with Anatase TiO2
    Ruthenium metal nanoparticles with a narrow size distribution have been synthesised via a solvothermal method. The solids were characterised using a range of analytical techniques (XRD, TEM, TPD, and XPS) and tested in the CO2+H2O reaction under simulated solar radiation, showing photocatalytic activity towards the production of CH4 and CO. The photocatalysis was promoted through a plasmonic excitation of the Ru. The addition of Ti to the preparation resulted in the formation of anatase TiO2. Notwithstanding the fact that the energy of the light used during the photocatalysis was insufficient to excite TiO2, its presence affects the catalysts’ optical and chemical properties and the product (CH4/CO) ratios, favouring the evolution of CO over that of CH4 (suggesting exciton transfer to TiO2 from plasmonically excited Ru).
      341Scopus© Citations 2
  • Publication
    Renewable energy technologies and its adaptation in an urban environment
    This general article is based on the inaugural talk delivered at the opening of OMTAT 2013 conference. It notes that the integration of renewable energy sources into living and transport sectors presents a daunting task, still. In spite of the fact that the earth and its atmosphere continually receive 1.7 × 1017 watts of radiation from the sun, in the portfolio of sustainable and environment friendly energy options, which is about 16% of the world’s energy consumption and mostly met by biomass, only a paltry 0.04% is accredited to solar. First and second generation solar cells offer mature technologies for applications. The most important difficulty with regards to integration with structures is not only the additional cost, but also the lack of sufficient knowledge in managing the available energy smartly and efficiently. The incorporation of PV as a part of building fabric greatly reduces the overall costs compared with retrofitting. BIPV (Building Integrated photovoltaic) is a critical technology for establishing aesthetically pleasing solar structures. Infusing PV and building elements is greatly simplified with some of the second generation thin film technologies now manufactured as flexible panels. The same holds true for 3rd generation technologies under development such as, and dye- and quantum dot- sensitized solar cells . Additionally, these technologies offer transparent or translucent solar cells for incorporation into windows and skylights. This review deals with the present state of solar cell technologies suitable for BIPV and the status of BIPV applications and its future prospects.
      2004Scopus© Citations 1
  • Publication
    First-principles study of the excited-state properties of coumarin-derived dyes in dye-sensitized solar cells
    Using Time-Dependent Density Functional Theory (TD-DFT), we have investigated the optical properties of dye-sensitized solar cells (DSSCs) comprised of TiO2 nanoparticle sensitized with two coumarins, namely, NKX-2311 and NKX-2593. The two sensitizers (dyes) differ only in their linker moieties and are shown to have different absorption spectra when adsorbed on to the TiO2 surface. Knowledge of different light absorption and charge transfer (CT) behavior within these complexes is useful for further improving the photo-dynamics of newer organic dyes presently being designed and investigated worldwide. Moreover, we have also investigated the effect of deprotonation of the sensitizers' carboxylic groups during adsorption on the titania surface and the excited state electronic properties of the resulting species.
      1267Scopus© Citations 52
  • Publication
    Succinonitrile-based solid-state electrolytes for dye-sensitised solar cells
    Succinonitrile (SCN), a solid ion conductor (10−4 to 10−3 S/cm) in solid form at room temperature, is mixed with either 1,2-dimethyl-3-propylimidazoliuum iodide or 1-butyl-3-methyl imidazolium iodide ionic liquids for forming a solid plastic phase electrolyte for use in dye-sensitised solar cell (DSSC). Cells containing these two electrolytes showed best energy conversion efficiencies of 6.3% and 5.6%, respectively. The commonly used DSSC electrolyte additives inhibit the formation of the SCN plastic phase. However, for the first time, an SCN-additive (additive = guanidinium thiocyanate) electrolyte composition is reported here, which remains as a solid at room temperatures. By using these new solid electrolytes, a simple and rapid single-step filling procedure for making solid-state DSSC is outlined. This process, which reduces the required manufacturing steps from four to one, is most suitable for continuous, high-throughput, commercial DSSC manufacturing lines. These new electrolytes have been tested under low incident light levels (200 lx) to investigate their suitability for indoor DSSC applications
      701Scopus© Citations 18
  • Publication
    Visible light active C-doped titanate nanotubes prepared via alkaline hydrothermal treatment of C-doped nanoparticulate TiO2: Photo-electrochemical and photocatalytic properties
    Carbon-doped titanate nanotubes (C-TNT) were formed via alkaline hydrothermal treatment of a TiO2 nanoparticulate material pre-doped with carbon. Attempts to form C and W co-doped titanate nanotubes using analogous C and W co-doped nanoparticulate materials were unsuccessful. Physical characterisations, such as X-ray diffraction, N2 physisorption and Transmission Electron Microscopy, confirmed the formation of titanate nanotubes ~7 nm in diameter and hundreds of nm in length with increased surface areas relative to the nanoparticulate precursors. X-ray Photoelectron Spectroscopy confirmed the retention of substitutional carbon dopant and the exclusion of tungsten dopant from the doped TNT materials. Converting doped (or undoped TiO2) into C-TNT (or TNT) slightly increases the material’s bandgap but the C-TNT material (in contrast to TNT and undoped TiO2) absorbs into the visible region of the spectrum. C-doped and un-doped titanate nanotube materials were more active in promoting the photo degradation of 4-chlorophenol under visible light than their analogous nanoparticulate precursors. C-TNT was the most photocatalytically active material tested. However, photocurrent response measurements showed C-TNT to be less effective at generating current following irradiation than both its nanoparticulate analogue and nanoparticulate P25 when screen printed onto electrode surfaces. We ascribe this to non-optimal alignment of the TNTs on the electrode surface.
      598Scopus© Citations 33
  • Publication
    Routes to visible light active C-doped TiO2 photocatalysts using carbon atoms from the Ti precursors
    In this work, different thermal treatments of titanium isopropoxide-derived photo-catalyst precursors, designed with the purpose of generating C-doped TiO2 photo-catalysts using carbon atoms present in the TiOx gel precursors as dopants, are presented. Specifically, these look at varying the standard calcination techniques using heat treatments in He (rather than calcination in air) and lower temperature calcinations (200 °C rather than 500 °C). The formed materials are characterised using N2 physisorption, XRD, UV Visible spectroscopy and XPS and their activities in promoting the oxidation of 4-chlorophenol under visible-light-only conditions were analysed. The nature of carbon remaining on the (or in the) material is discussed found to be both surface graphitic carbon and carbon present in anionic dopant positions. The different contributions of each type of carbon to the catalytic photo-activity under visible light are discussed.
      403Scopus© Citations 25
  • Publication
    A TD-DFT study of the effects of structural variations on the photochemistry of polyene dyes
    We report a TD-DFT study of three polyene dyes namely: NKX-2553, NKX-2554 and NKX-2569 in isolation as well as upon their adsorption on TiO2 nanoparticles. By choosing closely related dyes we wish to focus on the effects of structural variations on the absorption and charge-transfer properties of these systems. These three dyes show a non-intuitive trend in their respective efficiencies and therefore, were chosen to shed light on the structural components that contribute to this behaviour. Although, NKX-2554 has an additional donor group, it is less efficient compared to the simpler NKX-2553 dye that contains only one donor group. When NKX-2554 structure is slightly modified by lengthening the linker-group, one obtains the most efficient dye among this set, namely, NKX-2569. In this work, we show that the changes in the donor moiety has very little or no effect on the efficiency of these dyes as can be seen in the case of NKX-2553 and NKX-2554. On the other hand, the improved performance of NKX-2569-titania complex can be understood to be a result of the longer linker group. A better understanding of these properties within different dye-titania complexes is important for the continual improvement of DSSCs. In this regards, this study will serve to provide guidelines to improve efficiencies of novel organic dyes.
      782Scopus© Citations 39
  • Publication
    Scope for spherical Bi2WO6 quazi-perovskites in the artificial photosynthesis reaction – the effects of surface modification with amine groups
    The synthesis, characterisation, modification (with n-propyl amine groups) of Bi2WO6 particles and the scope for its application in artificial photosynthesis reactions is described. The synthesis involves microwave activation of spherical Bi2O3 precursors followed by a hydrothermal treatment in the presence of Na2WO4. These are characterised using electron microscopy (TEM and SEM), BET, XRD, FTIR, FT-Raman and UV-Visible spectroscopies and CO2 TPD. Subsequently this material is modified through the condensation of propyl amine groups to surface hydroxyl groups, and the composites prepared are characterised using FTIR and D-FTIR following exposure to CO2. Both the spherical particles and the amine-modified analogues are applied in the artificial photosynthesis reaction under batch conditions. O2, CO and CH4 are the observed gaseous products during the reaction and there is FTIR evidence for the formation of adsorbed alcohols and carbonylated products. Although the modification with amine groups decreased the overall photocatalytic reactivity, it also altered the product selectivity with respect to the CH4/CO ratio. The catalyst tends to improve the oxygen production ability after about 20h of operation, with a decline in CH4 and CO production, indicating that other condensates are probably generated. This opens up new possibilities and scope for this catalyst and further research is required to understand the observations.
      51Scopus© Citations 3