Christopher S. Blackman

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Organization: University College London , England
Department: Department of Chemistry
Title: (PhD)

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Co-reporter:Min Ling;Robert G. Palgrave;Carlos Sotelo-Vazquez;Andreas Kafizas;Ivan P. Parkin
Advanced Materials Interfaces 2017 Volume 4(Issue 18) pp:
Publication Date(Web):2017/09/01
DOI:10.1002/admi.201700064
Tungsten trioxide nanorod arrays are deposited using aerosol assisted chemical vapor deposition. The electronic structure, defect chemistry, optical bandgap, and photocatalytic activity are found to vary progressively with nanorod length. Nanorods less than 1 µm in length show a widening of the optical bandgap (up to 3.1 eV), more disorder states within the bandgap, an absence of reduced tungsten cation states, and increased photocatalytic activity for destruction of a test organic pollutant (stearic acid) compared to nanorods of 2 µm length or greater which possessed bandgaps close to the bulk value for tungsten oxide (2.6–2.8 eV), the presence of reduced tungsten states (W4+), and lower photocatalytic activity. The results indicate that for maximum photocatalytic performance in organic pollutant degradation, tungsten oxide should be engineered such that the bandgap is widened relative to bulk WO3 to a value above 3 eV; although less photons are expected be absorbed, increases in the overpotential for oxidation reactions appear to more than offset this loss. It is also desirable to ensure the material remains defect free, or the defect concentration minimized, to minimize carrier recombination.
Co-reporter:Fatima E. Annanouch, Z. Haddi, M. Ling, F. Di Maggio, S. Vallejos, T. Vilic, Y. Zhu, T. Shujah, P. Umek, C. Bittencourt, C. Blackman, and E. Llobet
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 16) pp:10413
Publication Date(Web):April 4, 2016
DOI:10.1021/acsami.6b00773
We report for the first time the successful synthesis of palladium (Pd) nanoparticle (NP)-decorated tungsten trioxide (WO3) nanoneedles (NNs) via a two-step aerosol-assisted chemical vapor deposition approach. Morphological, structural, and elemental composition analysis revealed that a Pd(acac)2 precursor was very suitable to decorate WO3 NNs with uniform and well-dispersed PdO NPs. Gas-sensing results revealed that decoration with PdO NPs led to an ultrasensitive and selective hydrogen (H2) gas sensor (sensor response peaks at 1670 at 500 ppm of H2) with low operating temperature (150 °C). The response of decorated NNs is 755 times higher than that of bare WO3 NNs. Additionally, at a temperature near that of the ambient temperature (50 °C), the response of this sensor toward the same concentration of H2 was 23, which is higher than that of some promising sensors reported in the literature. Finally, humidity measurements showed that PdO/WO3 sensors displayed low-cross-sensitivity toward water vapor, compared to bare WO3 sensors. The addition of PdO NPs helps to minimize the effect of ambient humidity on the sensor response.Keywords: aerosol-assisted CVD; gas sensor; nanoneedles; nanoparticles
Co-reporter:Savio J. A. Moniz, David Pugh, Christopher S. Blackman, Junwang Tang, and Claire J. Carmalt
Crystal Growth & Design 2016 Volume 16(Issue 7) pp:3818-3825
Publication Date(Web):May 24, 2016
DOI:10.1021/acs.cgd.6b00370
BiFeO3 is an interesting multifunctional narrow band gap semiconductor that exhibits simultaneous multiferroic, photovoltaic, and photocatalytic behavior. Hence there is much interest in the growth of thin films of BiFeO3 via chemical vapor deposition (CVD); however, the number of suitable bismuth precursors is severely limited. A series of homoleptic bismuth(III) β-diketonate complexes were synthesized via simple room temperature ligand-exchange reactions from [Bi(N(SiMe3)2)3] and free diketonate ligands, which yielded the crystal structure of [Bi(acac)3] as a 1-D polymer. We attempted to use these complexes for low pressure CVD (LPCVD) growth of BiFeO3 films with [Fe(acac)3]; however, all bismuth complexes exhibited poor volatilities and decomposition characteristics, and as a result film growth was unsuccessful. Subsequently, the volatile alkoxide [Bi(OtBu)3], with [Fe(acac)3], was used to grow dense BiFeO3 films via low pressure CVD. The BiFeO3 films possessed multiferroic properties at room temperature and exhibited activity for visible light-driven water oxidation in the presence of a Ag+ electron scavenger, which improved significantly when modified with a cobalt surface cocatalyst. The increase in activity, probed by time-resolved photoluminescence spectroscopy, was attributed to improved charge carrier separation arising from the in-built internal electric field of BiFeO3 in addition to the presence of an efficient cobalt oxygen evolution catalyst.
Co-reporter:Savio J. A. Moniz, Raul Quesada-Cabrera, Christopher S. Blackman, Junwang Tang, Paul Southern, Paul M. Weaver and Claire J. Carmalt  
Journal of Materials Chemistry A 2014 vol. 2(Issue 9) pp:2922-2927
Publication Date(Web):2013/12/20
DOI:10.1039/C3TA14824F
A novel method for preparation of BiFeO3 films via a simple solution-based CVD method is reported using for the first time a single-source heterobimetallic precursor [CpFe(CO)2BiCl2]. BiFeO3 films display ferroelectric and ferromagnetic ordering at room temperature and possess direct band-gaps between 2.0 and 2.2 eV. Photocatalytic testing for water oxidation revealed high activities under UVA (365 nm) and simulated solar irradiation, superior to that exhibited by a commercial standard (Pilkington Activ® TiO2 film) resulting in an apparent quantum yield of ∼24%.
Co-reporter:Stella Vallejos;Polona Umek;Toni Stoycheva;Fatima Annanouch;Eduard Llobet;Xavier Correig;Patrizia De Marco;Carla Bittencourt;Chris Blackman
Advanced Functional Materials 2013 Volume 23( Issue 10) pp:1313-1322
Publication Date(Web):
DOI:10.1002/adfm.201201871

Abstract

Tungsten oxide nanostructures functionalized with gold or platinum NPs are synthesized and integrated, using a single-step method via aerosol-assisted chemical vapour deposition, onto micro-electromechanical system (MEMS)-based gas-sensor platforms. This co-deposition method is demonstrated to be an effective route to incorporate metal nanoparticles (NP) or combinations of metal NPs into nanostructured materials, resulting in an attractive way of tuning functionality in metal oxides (MOX). The results show variations in electronic and sensing properties of tungsten oxide according to the metal NPs introduced, which are used to discriminate effectively analytes (C2H5OH, H2, and CO) that are present in proton-exchange fuel cells. Improved sensing characteristics, in particular to H2, are observed at 250 °C with Pt-functionalized tungsten oxide films, whereas non-functionalized tungsten oxide films show responses to low concentrations of CO at low temperatures. Differences in the sensing characteristics of these films are attributed to the different reactivities of metal NPs (Au and Pt), and to the degree of electronic interaction at the MOX/metal NP interface. The method presented in this work has advantages over other methods of integrating nanomaterials and devices, of having fewer processing steps, relatively low processing temperature, and no requirement for substrate pre-treatment.

Co-reporter:Stella Vallejos;Polona Umek;Toni Stoycheva;Fatima Annanouch;Eduard Llobet;Xavier Correig;Patrizia De Marco;Carla Bittencourt;Chris Blackman
Advanced Functional Materials 2013 Volume 23( Issue 10) pp:
Publication Date(Web):
DOI:10.1002/adfm.201370049
Co-reporter:Savio J. A. Moniz, Christopher S. Blackman, Claire J. Carmalt and Geoffrey Hyett  
Journal of Materials Chemistry A 2010 vol. 20(Issue 36) pp:7881-7886
Publication Date(Web):02 Aug 2010
DOI:10.1039/C0JM01720E
Bismuth(III) tert-butoxide [Bi(OtBu)3] was utilised as a single-source precursor to controllably deposit thin films of different phases of bismuth oxide (Bi2O3) on glass substrates via low-pressure chemical vapour deposition (LPCVD). Band gaps for the different phases have been measured (Eg = 2.3–3.0 eV) and the films displayed excellent photodegradation of water under near-UV irradiation.
Co-reporter:Christopher S. Blackman, C. Piccirillo, R. Binions, Ivan P. Parkin
Thin Solid Films 2009 Volume 517(Issue 16) pp:4565-4570
Publication Date(Web):30 June 2009
DOI:10.1016/j.tsf.2008.12.050
Atmospheric pressure chemical vapour deposition of VCl4, WCl6 and water at 550 °C lead to the production of high quality tungsten doped vanadium dioxide thin films. Careful control of the gas phase precursors allowed for tungsten doping up to 8 at.%. The transition temperature of the thermochromic switch was tunable in the range 55 °C to − 23 °C. The films were analysed using X-ray diffraction, scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Their optical properties were examined using variable-temperature transmission and reflectance spectroscopy. It was found that incorporation of tungsten into the films led to an improvement in the colour from yellow/brown to green/blue depending on the level of tungsten incorporation. The films were optimized for optical transmission, thermochromic switching temperature, magnitude of the switching behaviour and colour to produce films that are suitable for use as an energy saving environmental glass product.
Co-reporter:Savio J. A. Moniz, Raul Quesada-Cabrera, Christopher S. Blackman, Junwang Tang, Paul Southern, Paul M. Weaver and Claire J. Carmalt
Journal of Materials Chemistry A 2014 - vol. 2(Issue 9) pp:NaN2927-2927
Publication Date(Web):2013/12/20
DOI:10.1039/C3TA14824F
A novel method for preparation of BiFeO3 films via a simple solution-based CVD method is reported using for the first time a single-source heterobimetallic precursor [CpFe(CO)2BiCl2]. BiFeO3 films display ferroelectric and ferromagnetic ordering at room temperature and possess direct band-gaps between 2.0 and 2.2 eV. Photocatalytic testing for water oxidation revealed high activities under UVA (365 nm) and simulated solar irradiation, superior to that exhibited by a commercial standard (Pilkington Activ® TiO2 film) resulting in an apparent quantum yield of ∼24%.
Co-reporter:Savio J. A. Moniz, Christopher S. Blackman, Claire J. Carmalt and Geoffrey Hyett
Journal of Materials Chemistry A 2010 - vol. 20(Issue 36) pp:NaN7886-7886
Publication Date(Web):2010/08/02
DOI:10.1039/C0JM01720E
Bismuth(III) tert-butoxide [Bi(OtBu)3] was utilised as a single-source precursor to controllably deposit thin films of different phases of bismuth oxide (Bi2O3) on glass substrates via low-pressure chemical vapour deposition (LPCVD). Band gaps for the different phases have been measured (Eg = 2.3–3.0 eV) and the films displayed excellent photodegradation of water under near-UV irradiation.
Li2(MeNCH2CH2NMe)
Na(THF)(monomethylcyclopentadienyl)
Tetrakis(dimethylamino)vanadium
molybdenum,tetrabutylammonium,hexacosahydrate
Phenol, tungsten(6+) salt
Bismuth,tris(2,4-pentanedionato-kO,kO')-, (OC-6-11)- (9CI)
Arsine,(1,1-dimethylethyl)-
Titanium tungsten oxide
Gallium, trimethyl-
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