Now showing 1 - 10 of 11
  • Publication
    Evaluation of microwave plasma oxidation treatments for the fabrication of photoactive un-doped and carbon-doped TiO2 coatings
    The photoactivity of both un-doped and carbon-doped titanium dioxide (TiO2) coatings has been widely reported. In this paper, the use of a microwave plasma as a novel oxidation treatment for the fabrication of these coatings is evaluated. The photoactivity performance of the microwave plasma-formed coatings is benchmarked against those fabricated through air furnace oxidation as well as those deposited using reactive magnetron sputtering. The un-doped and carbon-doped TiO2 coatings were prepared respectively by microwave plasma-oxidizing titanium metal sheets and sputter deposited titanium carbide thin films. The resulting oxides were characterized using XPS, XRD, FEG-SEM, and optical profilometry. The oxide layer thicknesses achieved over the 15 to 45 minute oxidation times were in the range of 0.15 to 3.44 µm. These coatings were considerably thicker than those obtained by air furnace oxidation. The microwave plasma-formed oxides also exhibited significantly higher surface roughness values compared with the magnetron-sputtered coatings. The photoactivity performance of both un-doped and carbon-doped coatings was assessed using photocurrent density measurements. Comparing the un-doped TiO2 coatings, it was observed that those obtained using the microwave plasma oxidation route yielded photocurrent density measurements that were 4.3 times higher than the TiO2 coatings of the same thickness that were deposited by sputtering. The microwave plasma-oxidized titanium carbide coatings did not perform as well as the un-doped TiO2 probably due to the presence of un-oxidized carbide in the coatings, which reduced their photoactivity.
      1419Scopus© Citations 33
  • 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.
      872Scopus© Citations 108
  • Publication
    Deposition and characterization of NiOx coatings by magnetron sputtering for application in dye-sensitized solar cells
    Nickel oxide (NiOx) due to its p-type nature has considerable potential as a photocathodic material in energy conversion devices such as dye-sensitized solar cells (DSSCs). However,NiOx has not been extensively used for this application mainly because of low light harvesting efficiency due to limited dye loading on the coatings. In this study NiOx coatings were deposited using the dc- magnetron sputtering technique from a nickel target in an argon/oxygen plasma. One of the advantages of magnetron sputtering is the ability to control coating properties such as mechanical performance and chemical stoichiometry. It is anticipated that by enhancing the interconnectivity between NiOx particles and by optimizing surface roughness, it may be possible to enhance dye adsorption and increase its ability to absorb visible light. NiOx coatings were deposited onto both silicon wafer and indium tin oxide (ITO) covered glass substrates. The influence of deposition parameters such as pressure, nickel target current and substrate bias voltage were correlated with the coating properties of surface roughness, thickness, crystallographic structure and surface energy. This evaluation was carried out using optical profilometry, spectroscopic ellipsometry, XRD and contact angle measurements respectively. It was observed that deposited coating morphology and roughness were significantly influenced by the deposition parameters. For example increasing the deposition pressure from 0.20 to 0.40 Pa led to an increase in surface roughness (Ra) from 1.6 to 3 nm. Associated with this increase in roughness the surface energy increased from 36 to 61 mN/mm. The NiOx coatings were spectrally sensitized with Rucomplex dye containing -COOH groups as anchoring moieties. The dye adsorptions on NiOx coatings, deposited on ITO substrates, were investigated in transmission mode using UV-vis spectroscopy in the range of 400 – 800 nm. It was observed that for the coatings with the highest surface energy, there was an increase of up to 60 % in the level of dye adsorption. The electroactivity of the NiOx thin films deposited on Ni substrate at 0.4 Pa has been verified through the occurrence of redox processes of reduction and lithium intercalation within the oxide film.
      7258Scopus© Citations 58
  • Publication
    Activation of hematite nanorod arrays for photoelectrochemical water splitting
    Hematite nanorod arrays were activated through proper control of annealing conditions. The 100-fold improvement in photocurrent was correlated with increased absorption and Sn doping from the tin oxide coated glass substrate. The low onset potential is attributed to a reduction in surface defects, while the morphology is credited for promoting tin diffusion and facilitating electron transport.
      2114Scopus© Citations 153
  • Publication
    Influence of doping on the photoactive properties of magnetron-sputtered titania coatings: Experimental and theoretical study
    (American Physical Society, 2012-09) ; ; ;
    Titanium dioxide (TiO2) thin films, doped with chromium (Cr) and codoped with chromium-carbon (Cr, C) and chromium-nitrogen (Cr, N) of various concentrations, were deposited using magnetron sputtering. Postdeposition thermal treatments were carried out at 450 ◦C for 5 h to change the as-deposited amorphous coatings to their crystalline form. The crystalline phase was found to be dependent on the amount and type of dopant present. Ultraviolet-visible (UV-Vis) absorption data and band gap energies calculated by spectroscopic ellipsometry showed that, on increasing Cr concentration, a shift of the absorption edge towards visible light and a reduction of the band gap occurred. This was further improved by codoping of Cr with either N or C, with the latter case exhibiting more photo-activity towards visible light. In addition, hybrid density functional theory (DFT) calculations were performed for Cr-, N-. and C-monodoping, together with Cr-C and Cr-N codoping, in both rutile and anatase phases of crystalline titania. Using this method, absorption coefficients and band gaps were determined to explore photo-activity. Very good, semiquantitative agreement was found between the DFT and experimental approaches for these quantities, underlining the key role of state-of-the-art quantum calculations in interpreting and guiding experimental studies of doping in metal oxides.
      568Scopus© Citations 22
  • Publication
    Application of a novel microwave plasma treatment for the sintering of nickel oxide coatings for use in dye-sensitized solar cells
    In this study the use of microwave plasma sintering of nickel oxide (NiOx) particles for use as p-type photoelectrode coatings in dye-sensitized solar cells (DSSCs) is investigated. NiOx was chosen as the photocathode for this application due to its stability, wide band gap and p-type nature. For high light conversion efficiency DSSCs require a mesoporous structure exhibiting a high surface area. This can be achieved by sintering particles of NiOx onto a conductive substrate. In this study the use of both 2.45 GHz microwave plasma and conventional furnace sintering were compared for the sintering of the NiOx particles. Coatings 1 to 2.5 μm thick were obtained from the sintered particles (mean particle size of 50 nm) on 3 mm thick fluorine-doped tin oxide (FTO) coated glass substrates. Both the furnace and microwave plasma sintering treatments were carried out at ~ 450 °C over a 5 minute period. Dye sensitization was carried out using Erythrosin B and the UV-vis absorption spectra of the NiOx coatings were compared. A 44% increase in the level of dye adsorption was obtained for the microwave plasma sintered samples as compared to that obtained through furnace treatments. While the photovoltaic performance of the DSSC fabricated using the microwave plasma treated NiOx coatings exhibited a tenfold increase in the conversion efficiency in comparison to the furnace treated samples. This enhanced performance was associated with the difference in the mesoporous structure of the sintered NiOx coatings.
      2416Scopus© Citations 44
  • Publication
    Spray deposited NiOx films on ITO substrates as photoactive electrodes for p-type dye-sensitized solar cells
    Spray deposition followed by sintering of nickel oxide (NiO x ) nanoparticles (average diameter: 40 nm) has been chosen as method of deposition of mesoporous NiO x coatings onto indium tin oxide (ITO) substrates. This procedure allows the scalable preparation of NiO x samples with large surface area (~103 times the geometrical area) and its potential for applications such as electrocatalysis or electrochemical solar energy conversion, which require high electroactivity in confined systems. The potential of these NiO x films as semiconducting cathodes for dye-sensitized solar cell (DSC) purposes has been evaluated for 0.3–3-μm-thick films of NiO x sensitized with erythrosine B (ERY). The electrochemical processes involving the NiO x coatings in the pristine and sensitized states were examined and indicated surface confinement as demonstrated by the linear dependence of the current densities with the scan rate of the cyclic voltammetry. Cathodic polarization of NiO x on ITO can also lead to the irreversible reduction of the underlying ITO substrate because of the mesoporous nature of the sintered NiO x film that allows the shunting of ITO to the electrolyte. ITO-based reduction processes alter irreversibly the properties of charge transfer through the ITO/NiOx interface and limit the range of potential to NiO x coatings sintered for DSC purposes.
      714Scopus© Citations 35
  • Publication
    Photolytic water oxidation catalyzed by a molecular carbene iridium complex
    The complex IrCl2(Cp*)(trz) (trz = triazolylidene), 2, was prepared from readily available 1,3-dimethyl-4-phenyl-1,2,3-triazolium salt. Under basic conditions, the C-bound phenyl group readily cyclometalates, while under acidic conditions, cyclometalation is reversed. The sensitivity of the Caryl–Ir bond but not the Ctrz–Ir bond towards acidolysis provided a basis for using 2 as a catalyst in CeIV-mediated water oxidation. The catalytic activity is characterized by a robust catalytic cycle, affording excellent turnover numbers (TON > 20 000). Under cerium-free conditions and in the presence of hematite as a photoelectrode, light-induced activity was observed. The photoelectrochemical reaction is strongly pH-dependent, which requires pH adjustments when running multiple cycle experiments to regenerate the catalytic activity. Analogous chelating complexes display better stability and higher catalytic activity than the monodentate complex 2.
      406Scopus© Citations 92
  • Publication
    Photo-active and dynamical properties of hematite (Fe2O3)-water interfaces: An experimental and theoretical study
    The dynamical properties of physically and chemically adsorbed water molecules at pristine hematite-(001) surfaces have been studied by means of equilibrium Born–Oppenheimer molecular dynamics (BOMD) in the NVT ensemble at 298 K. The dissociation of water molecules to form chemically adsorbed species was scrutinised, in addition to ‘hopping’ or swapping events of protons between water molecules. Particular foci have been dynamical properties of the adsorbed water molecules and OH− and H3O+ ions, the hydrogen bonds between protons in water molecules and the bridging oxygen atoms at the hematite surface, as well as the interactions between oxygen atoms in adsorbed water molecules and iron atoms at the hematite surface. Experimental results for photoelectrical current generation complement simulation findings of water dissociation.
      455Scopus© Citations 26
  • Publication
    The influence of Ti and Si doping on the structure, morphology and photo-response properties of α-Fe2O3 for efficient water splitting: experiment and first-principle calculations
    Ti- and Si- doping effects on morphology, structure, optical and photo-response of α-Fe2O3 nanoscale coatings from atmospheric-pressure chemical vapour deposition (APCVD) have been studied. Si- and Ti-doping led to larger clusters with finer grains and smaller clusters with larger grains, respectively. Photocurrent performance was increased remarkably by doping, especially Si. Excellent agreement was found for band gaps and optical properties compared to hybrid-Density Functional Theory. Substitutional replacement of Fe by Si shrinks the volume more than Ti-doping; it is conjectured that this affects hopping probability of localised charge-carriers more and leads to enhanced photocurrent activity for Si-doping, supported by experiment.
      554Scopus© Citations 17