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  • Journal article
    Chadwick NP, Kafizas A, Quesada-Cabrera R, Sotelo-Vazquez C, Bawaked SM, Mokhtar M, Al Thabaiti SA, Obaid AY, Basahel SN, Durrant JR, Carmalt CJ, Parkin IPet al., 2017,

    Ultraviolet Radiation Induced Dopant Loss in a TiO2 Photocatalyst

    , ACS CATALYSIS, Vol: 7, Pages: 1485-1490, ISSN: 2155-5435
  • Book chapter
    Kafizas A, Godin R, Durrant JR, 2017,

    Charge Carrier Dynamics in Metal Oxide Photoelectrodes for Water Oxidation

    , SEMICONDUCTORS FOR PHOTOCATALYSIS, Editors: Mi, Wang, Jagadish, Publisher: ELSEVIER ACADEMIC PRESS INC, Pages: 3-46
  • Journal article
    Sathasivam S, Williamson BAD, Kafizas A, Althabaiti SA, Obaid AY, Basahel SN, Scanlon DO, Carmalt CJ, Parkin IPet al., 2016,

    Computational and experimental study of Ta2O5 thin films

    , Journal of Physical Chemistry C, Vol: 121, Pages: 202-210, ISSN: 1932-7447

    This paper reports the novel synthesis of amorphous Ta2O5 and the subsequent isolation of the orthorhombic (β) crystallographic phase, using aerosol-assisted chemical vapor deposition. Hybrid density functional theory was used to obtain the calculated optical band gap (3.83 eV) for the first time, which closely matches our experimental findings (3.85 eV). The films were highly transparent in the visible and near-IR region of the electromagnetic spectrum. The refractive indexes, calculated using the Swanepoel method, showed good agreement with literature findings. The photocatalytic properties of the films, determined through the photominerilization of stearic acid under 254 nm radiation showed the amorphous sample to be an order of magnitude superior over crystalline β-Ta2O5.
  • Journal article
    Sachs M, Pastor E, Kafizas A, Durrant JRet al., 2016,

    Evaluation of Surface State Mediated Charge Recombination in Anatase and Rutile TiO2

    , Journal of Physical Chemistry Letters, Vol: 7, Pages: 3742-3746, ISSN: 1948-7185

    In nanostructured thin films, photogeneratedcharge carriers can access the surface more easily than indense films and thus react more readily. However, the highsurface area of these films has also been associated withenhanced recombination losses via surface states. We hereinuse transient absorption spectroscopy to compare the ultrafastcharge carrier kinetics in dense and nanostructured TiO2films for its two most widely used polymorphs: anatase andrutile. We find that nanostructuring does not enhance recombinationrates on ultrafast timescales, indicating thatsurface state mediated recombination is not a key loss pathwayfor either TiO2 polymorph. Rutile shows faster, and lessintensity-dependent recombination than anatase, which weassign to its higher doping density. For both polymorphs, weconclude that bulk rather than surface recombination is theprimary determinant of charge carrier lifetime.
  • Journal article
    Ma Y, Mesa CA, Pastor E, Kafizas A, Francas L, Le Formal F, Pendlebury SR, Durrant JRet al., 2016,

    Rate law analysis of water oxidation and hole scavenging on a BiVO4 photoanode

    , ACS Energy Letters, Vol: 1, Pages: 618-623, ISSN: 2380-8195

    Spectroelectrochemical studies employing pulsed LED irradiation are used to investigate the kinetics of water oxidation on undoped dense bismuth vanadate (BiVO4) photoanodes under conditions of photoelectrochemical water oxidation and compare to those obtained for oxidation of a simple redox couple. These measurements are employed to determine the quasi-steady-state densities of surface-accumulated holes, ps, and correlate these with photocurrent density as a function of light intensity, allowing a rate law analysis of the water oxidation mechanism. The reaction order in surface hole density is found to be first order for ps < 1 nm–2 and third order for ps > 1 nm–2. The effective turnover frequency of each surface hole is estimated to be 14 s–1 at AM 1.5 conditions. Using a single-electron redox couple, potassium ferrocyanide, as the hole scavenger, only the first-order reaction is observed, with a higher rate constant than that for water oxidation. These results are discussed in terms of catalysis by BiVO4 and implications for material design strategies for efficient water oxidation.
  • Journal article
    Ma Y, Kafizas A, Pendlebury SR, Le Formal F, Durrant JRet al., 2016,

    Photoinduced Absorption Spectroscopy of CoPi on BiVO4: The Function of CoPi during Water Oxidation

    , Advanced Functional Materials, Vol: 26, Pages: 4951-4960, ISSN: 1616-301X

    This paper employs photoinduced absorption and electrochemical techniques to analyze the charge carrier dynamics that drive photoelectrochemical water oxidation on bismuth vanadate (BiVO4), both with and without cobalt phosphate (CoPi) co-catalyst. These results are correlated with spectroelectrochemical measurements of CoII oxidation to CoIII in a CoPi/FTO (fluorine doped tin oxide) electrode during dark electrocatalytic water oxidation. Electrocatalytic water oxidation exhibits a non-linear dependence on CoIII density, with a sharp onset at 1 × 1017 CoIII cm−2. These results are compared quantitatively with the degree of CoPi oxidation observed under conditions of photoinduced water oxidation on CoPi–BiVO4 photoanodes. For the CoPi–BiVO4 photoanodes studied herein, ≤5% of water oxidation proceeds from CoPi sites, making the BiVO4 surface the predominant water oxidation site. This study highlights two key factors that limit the ability of CoPi to improve the catalytic performance of BiVO4: 1) the kinetics of hole transfer from the BiVO4 to the CoPi layer are too slow to effectively compete with direct water oxidation from BiVO4; 2) the slow water oxidation kinetics of CoPi result in a large accumulation of CoIII states, causing an increase in recombination. Addressing these factors will be essential for improving the performance of CoPi on photoanodes for solar-driven water oxidation.
  • Journal article
    Kafizas A, Wang X, Pendlebury SR, Barnes P, Ling M, Sotelo-Vazquez C, Quesada-Cabrera R, Li C, Parkin IP, Durrantt JRet al., 2016,

    Where Do Photogenerated Holes Go in Anatase:Rutile TiO<sub>2</sub>? A Transient Absorption Spectroscopy Study of Charge Transfer and Lifetime

    , JOURNAL OF PHYSICAL CHEMISTRY A, Vol: 120, Pages: 715-723, ISSN: 1089-5639
  • Journal article
    Ma Y, Le Formal F, Kafizas A, Pendlebury S, Durrant Jet al., 2015,

    Efficient suppression of back electron/hole recombination in cobalt phosphate surface-modified undoped bismuth vanadate photoanodes

    , Journal of Materials Chemistry A, Vol: 3, Pages: 20649-20657, ISSN: 2050-7496

    In this paper, we compared for the first time the dynamics of photogenerated holes in BiVO4 photoanodes with and without CoPi surface modification, employing transient absorption and photocurrent measurements on microsecond to second timescales. CoPi surface modification is known to cathodically shift the water oxidation onset potential; however, the reason for this improvement has not until now been fully understood. The transient absorption and photocurrent data were analyzed using a simple kinetic model, which allows quantification of the competition between electron/hole recombination and water oxidation. The results of this model are shown to be in excellent agreement with the measured photocurrent data. We demonstrate that the origin of the improvement of photocurrent onset resulting from CoPi treatment is primarily due to retardation of back electron/hole recombination across the space charge layer; no evidence of catalytic water oxidation via CoPi was observed.
  • Journal article
    Wang X, Kafizas A, Li X, Moniz SJA, Reardon PJT, Tang J, Parkin IP, Durrant JRet al., 2015,

    Transient Absorption Spectroscopy of Anatase and Rutile: The Impact of Morphology and Phase on Photocatalytic Activity

    , JOURNAL OF PHYSICAL CHEMISTRY C, Vol: 119, Pages: 10439-10447, ISSN: 1932-7447
  • Journal article
    Kafizas AG, Durrant JR, 2015,

    Transient Absorption Spectroscopy of Anatase and Rutile: the Impact of Morphology and Phase on Photocatalytic Activity

    , The Journal of Physical Chemistry C, ISSN: 1932-7447
  • Journal article
    Sotelo-Vazquez C, Noor N, Kafizas A, Quesada-Cabrera R, Scanlon DO, Taylor A, Durrant JR, Parkin IPet al., 2015,

    Multifunctional P-Doped TiO2 films: a new approach to self-cleaning, transparent conducting oxide materials

    , Chemistry of Materials, Vol: 27, Pages: 3234-3242, ISSN: 1520-5002

    Multifunctional P-doped TiO2 thin films were synthesized by atmospheric pressure chemical vapor deposition (APCVD). This is the first example of P-doped TiO2 films with both P5+ and P3– states, with the relative proportion being determined by synthesis conditions. This technique to control the oxidation state of the impurities presents a new approach to achieve films with both self-cleaning and TCO properties. The origin of electrical conductivity in these materials was correlated to the incorporation of P5+ species, as suggested by Hall Effect probe measurements. The photocatalytic performance of the films was investigated using the model organic pollutant, stearic acid, with films containing predominately P3– states found to be vastly inferior photocatalysts compared to undoped TiO2 films. Transient absorption spectroscopy studies also showed that charge carrier concentrations increased by several orders of magnitude in films containing P5+ species only, whereas photogenerated carrier lifetimes—and thus photocatalytic activity—were severely reduced upon incorporation of P3– species. The results presented here provide important insights on the influence of dopant nature and location within a semiconductor structure. These new P-doped TiO2 films are a breakthrough in the development of multifunctional advanced materials with tuned properties for a wide range of applications.
  • Journal article
    Pendlebury SR, Wang X, Le Formal F, Cornuz M, Kafizas A, Tilley SD, Graetzel M, Durrant JRet al., 2014,

    Ultrafast charge carrier recombination and trapping in hematite photoanodes under applied bias

    , Journal of the American Chemical Society, Vol: 136, Pages: 9854-9857, ISSN: 0002-7863

    Transient absorption spectroscopy on subpicosecond to second time scales is used to investigate photogenerated charge carrier recombination in Si-doped nanostructured hematite (α-Fe2O3) photoanodes as a function of applied bias. For unbiased hematite, this recombination exhibits a 50% decay time of ∼6 ps, ∼103 times faster than that of TiO2 under comparable conditions. Anodic bias significantly retards hematite recombination dynamics, and causes the appearance of electron trapping on ps−μs time scales. These ultrafast recombination dynamics, their retardation by applied bias, and the associated electron trapping are discussed in terms of their implications for efficient water oxidation.
  • Journal article
    Knapp CE, Manzi JA, Kafizas A, Parkin IP, Carmalt CJet al., 2014,

    Aerosol-Assisted Chemical Vapour Deposition of Transparent Zinc Gallate Films

    , CHEMPLUSCHEM, Vol: 79, Pages: 1024-1029, ISSN: 2192-6506
  • Journal article
    Chadwick N, Sathasivam S, Kafizas A, Bawaked SM, Obaid AY, Al-Thabaiti S, Basahel SN, Parkin IP, Carmalt CJet al., 2014,

    Combinatorial aerosol assisted chemical vapour deposition of a photocatalytic mixed SnO2/TiO2 thin film

    , JOURNAL OF MATERIALS CHEMISTRY A, Vol: 2, Pages: 5108-5116, ISSN: 2050-7488
  • Journal article
    Kafizas A, Noor N, Carmichael P, Scanlon DO, Carmalt CJ, Parkin IPet al., 2014,

    Combinatorial Atmospheric Pressure Chemical Vapor Deposition of F: TiO 2; the Relationship between Photocatalysis and Transparent Conducting Oxide Properties

    , ADVANCED FUNCTIONAL MATERIALS, Vol: 24, Pages: 1758-1771, ISSN: 1616-301X
  • Journal article
    Sathasivam S, Kafizas A, Ponja S, Chadwick N, Bhachu DS, Bawaked SM, Obaid AY, Al-Thabaiti S, Basahel SN, Carmalt CJ, Parkin IPet al., 2014,

    Combinatorial Atmospheric Pressure CVD of a Composite TiO<sub>2</sub>/SnO<sub>2</sub> Thin Film

    , CHEMICAL VAPOR DEPOSITION, Vol: 20, Pages: 69-79, ISSN: 0948-1907
  • Journal article
    Kafizas A, Carmalt CJ, Parkin IP, 2013,

    CVD and precursor chemistry of transition metal nitrides

    , COORDINATION CHEMISTRY REVIEWS, Vol: 257, Pages: 2073-2119, ISSN: 0010-8545
  • Journal article
    O'Keeffe C, Gannon P, Gilson P, Kafizas A, Parkin IP, Binions Ret al., 2013,

    Air purification by heterogeneous photocatalytic oxidation with multi-doped thin film titanium dioxide

    , THIN SOLID FILMS, Vol: 537, Pages: 131-136, ISSN: 0040-6090
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    • Citations: 11
  • Journal article
    Wilkinson M, Kafizas A, Bawaked SM, Obaid AY, Al-Thabaiti SA, Basahel SN, Carmalt CJ, Parkin IPet al., 2013,

    Combinatorial Atmospheric Pressure Chemical Vapor Deposition of Graded TiO<sub>2</sub>-VO<sub>2</sub> Mixed-Phase Composites and Their Dual Functional Property as Self-Cleaning and Photochromic Window Coatings

    , ACS COMBINATORIAL SCIENCE, Vol: 15, Pages: 309-319, ISSN: 2156-8952
  • Book chapter
    Parkin IP, Kafizas A, 2013,

    Exothermic Metathesis Reactions

    , Comprehensive Inorganic Chemistry II Second Edition from Elements to Applications, Pages: 471-490

    The development of solid-state metathesis (SSM) routes over the last two decades has revolutionized the way in which several industrially important refractory ceramics, intermetallics, and semiconductors are made. In this chapter, the development of SSM routes in synthesizing a range of materials including metal borides and aluminides, carbides and silicides, nitrides, phosphides, arsenides and antimonides, oxides and sulfides, selenides and tellurides is covered. In addition, an overview of the new directions in metathesis is presented, including carbon nanotube and nanocrystal formation. © 2013 Elsevier Ltd. All rights reserved.

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Dr. Andreas Kafizas
Leader - Solar Coatings Group

e-mail: a.kafizas@imperial.ac.uk
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