Bismuth oxyhalides: Synthesis, structure and photoelectrochemical activity

Davinder S. Bhachu; Savio J.A. Moniz; Sanjayan Sathasivam; David O. Scanlon; Aron Walsh; Salem M. Bawaked; Mohamed Mokhtar; Abdullah Y. Obaid; Ivan P. Parkin; Junwang Tang; Claire J. Carmalt

doi:10.1039/c6sc00389c

Bismuth oxyhalides: Synthesis, structure and photoelectrochemical activity

Davinder S. Bhachu, Savio J.A. Moniz, Sanjayan Sathasivam, David O. Scanlon, Aron Walsh, Salem M. Bawaked, Mohamed Mokhtar, Abdullah Y. Obaid, Ivan P. Parkin, Junwang Tang, Claire J. Carmalt^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

We report the synthesis and photoelectrochemical assessment of phase pure tetragonal matlockite structured BiOX (where X = Cl, Br, I) films. The materials were deposited using aerosol-assisted chemical vapour deposition. The measured optical bandgaps of the oxyhalides, supported by density functional theory calculations, showed a red shift with the increasing size of halide following the binding energy of the anion p-orbitals that form the valence band. Stability and photoelectrochemical studies carried out without a sacrificial electron donor showed the n-type BiOBr film to have the highest photocurrent reported for BiOBr in the literature to date (0.3 mA cm^-2 at 1.23 V vs. RHE), indicating it is an excellent candidate for solar fuel production with a very low onset potential of 0.2 V vs. RHE. The high performance was attributed to the preferred growth of the film in the [011] direction, as shown by X-ray diffraction, leading to internal electric fields that minimize charge carrier recombination.

Original language	English
Pages (from-to)	4832-4841
Number of pages	10
Journal	Chemical Science
Volume	7
Issue number	8
DOIs	https://doi.org/10.1039/c6sc00389c
Publication status	Published - 2016

Bibliographical note

Funding Information:
I. P. P. and C. J. C. acknowledge EPSRC for funding the work under Grant EP/L017709. D. S. B. acknowledges Mr Kevin Reeves for assistance with SEM. Thank you to Pilkington NSG for the glass substrates. This work made use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk), via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), the Iridis cluster, provided by the EPSRC funded Centre for Innovation (Grant codes EP/K000144/1 and EP/K000136/1) and the UCL Legion HPC Facility (Legion@UCL). Thanks to Dr Ainara Garcia Gallastegui for useful discussions. S. S. acknowledges the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah for funding the work under grant D-1-434. D. O. S. acknowledges EPSRC for funding the work under grant EP/N01572X/1. The work at Bath was supported by the ERC (Grant no. 277757) and the EPSRC (Grant no. EP/K016288/1, EP/L017792/1 and EP/M009580/1). S. M. and J. T. acknowledge funding from EU FP7 4G-PHOTOCAT Grant no. 309636.

Publisher Copyright:
© 2016 The Royal Society of Chemistry.

ASJC Scopus subject areas

General Chemistry

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@article{d1a7e6e7d1094baa87a7bcb3003b7827,

title = "Bismuth oxyhalides: Synthesis, structure and photoelectrochemical activity",

abstract = "We report the synthesis and photoelectrochemical assessment of phase pure tetragonal matlockite structured BiOX (where X = Cl, Br, I) films. The materials were deposited using aerosol-assisted chemical vapour deposition. The measured optical bandgaps of the oxyhalides, supported by density functional theory calculations, showed a red shift with the increasing size of halide following the binding energy of the anion p-orbitals that form the valence band. Stability and photoelectrochemical studies carried out without a sacrificial electron donor showed the n-type BiOBr film to have the highest photocurrent reported for BiOBr in the literature to date (0.3 mA cm-2 at 1.23 V vs. RHE), indicating it is an excellent candidate for solar fuel production with a very low onset potential of 0.2 V vs. RHE. The high performance was attributed to the preferred growth of the film in the [011] direction, as shown by X-ray diffraction, leading to internal electric fields that minimize charge carrier recombination.",

author = "Bhachu, {Davinder S.} and Moniz, {Savio J.A.} and Sanjayan Sathasivam and Scanlon, {David O.} and Aron Walsh and Bawaked, {Salem M.} and Mohamed Mokhtar and Obaid, {Abdullah Y.} and Parkin, {Ivan P.} and Junwang Tang and Carmalt, {Claire J.}",

note = "Funding Information: I. P. P. and C. J. C. acknowledge EPSRC for funding the work under Grant EP/L017709. D. S. B. acknowledges Mr Kevin Reeves for assistance with SEM. Thank you to Pilkington NSG for the glass substrates. This work made use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk), via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), the Iridis cluster, provided by the EPSRC funded Centre for Innovation (Grant codes EP/K000144/1 and EP/K000136/1) and the UCL Legion HPC Facility (Legion@UCL). Thanks to Dr Ainara Garcia Gallastegui for useful discussions. S. S. acknowledges the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah for funding the work under grant D-1-434. D. O. S. acknowledges EPSRC for funding the work under grant EP/N01572X/1. The work at Bath was supported by the ERC (Grant no. 277757) and the EPSRC (Grant no. EP/K016288/1, EP/L017792/1 and EP/M009580/1). S. M. and J. T. acknowledge funding from EU FP7 4G-PHOTOCAT Grant no. 309636. Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

doi = "10.1039/c6sc00389c",

language = "English",

volume = "7",

pages = "4832--4841",

journal = "Chemical Science",

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T2 - Synthesis, structure and photoelectrochemical activity

AU - Bhachu, Davinder S.

AU - Moniz, Savio J.A.

AU - Sathasivam, Sanjayan

AU - Scanlon, David O.

AU - Walsh, Aron

AU - Bawaked, Salem M.

AU - Mokhtar, Mohamed

AU - Obaid, Abdullah Y.

AU - Parkin, Ivan P.

AU - Tang, Junwang

AU - Carmalt, Claire J.

N1 - Funding Information: I. P. P. and C. J. C. acknowledge EPSRC for funding the work under Grant EP/L017709. D. S. B. acknowledges Mr Kevin Reeves for assistance with SEM. Thank you to Pilkington NSG for the glass substrates. This work made use of the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk), via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), the Iridis cluster, provided by the EPSRC funded Centre for Innovation (Grant codes EP/K000144/1 and EP/K000136/1) and the UCL Legion HPC Facility (Legion@UCL). Thanks to Dr Ainara Garcia Gallastegui for useful discussions. S. S. acknowledges the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah for funding the work under grant D-1-434. D. O. S. acknowledges EPSRC for funding the work under grant EP/N01572X/1. The work at Bath was supported by the ERC (Grant no. 277757) and the EPSRC (Grant no. EP/K016288/1, EP/L017792/1 and EP/M009580/1). S. M. and J. T. acknowledge funding from EU FP7 4G-PHOTOCAT Grant no. 309636. Publisher Copyright: © 2016 The Royal Society of Chemistry.

PY - 2016

Y1 - 2016

N2 - We report the synthesis and photoelectrochemical assessment of phase pure tetragonal matlockite structured BiOX (where X = Cl, Br, I) films. The materials were deposited using aerosol-assisted chemical vapour deposition. The measured optical bandgaps of the oxyhalides, supported by density functional theory calculations, showed a red shift with the increasing size of halide following the binding energy of the anion p-orbitals that form the valence band. Stability and photoelectrochemical studies carried out without a sacrificial electron donor showed the n-type BiOBr film to have the highest photocurrent reported for BiOBr in the literature to date (0.3 mA cm-2 at 1.23 V vs. RHE), indicating it is an excellent candidate for solar fuel production with a very low onset potential of 0.2 V vs. RHE. The high performance was attributed to the preferred growth of the film in the [011] direction, as shown by X-ray diffraction, leading to internal electric fields that minimize charge carrier recombination.

AB - We report the synthesis and photoelectrochemical assessment of phase pure tetragonal matlockite structured BiOX (where X = Cl, Br, I) films. The materials were deposited using aerosol-assisted chemical vapour deposition. The measured optical bandgaps of the oxyhalides, supported by density functional theory calculations, showed a red shift with the increasing size of halide following the binding energy of the anion p-orbitals that form the valence band. Stability and photoelectrochemical studies carried out without a sacrificial electron donor showed the n-type BiOBr film to have the highest photocurrent reported for BiOBr in the literature to date (0.3 mA cm-2 at 1.23 V vs. RHE), indicating it is an excellent candidate for solar fuel production with a very low onset potential of 0.2 V vs. RHE. The high performance was attributed to the preferred growth of the film in the [011] direction, as shown by X-ray diffraction, leading to internal electric fields that minimize charge carrier recombination.

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U2 - 10.1039/c6sc00389c

DO - 10.1039/c6sc00389c

M3 - Article

AN - SCOPUS:84964725226

SN - 2041-6520

VL - 7

SP - 4832

EP - 4841

JO - Chemical Science

JF - Chemical Science

IS - 8

ER -

Bismuth oxyhalides: Synthesis, structure and photoelectrochemical activity

Abstract

Bibliographical note

ASJC Scopus subject areas

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