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Crystal Chemistry, Band-Gap Red Shift, and Electrocatalytic Activity of Iron-Doped Gallium Oxide Ceramics
[Image: see text] This work for the first time unfurls the fundamental mechanisms and sets the stage for an approach to derive electrocatalytic activity, which is otherwise not possible, in a traditionally known wide band-gap oxide material. Specifically, we report on the tunable optical properties,...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6963903/ https://www.ncbi.nlm.nih.gov/pubmed/31956757 http://dx.doi.org/10.1021/acsomega.9b01604 |
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author | Mallesham, Bandi Roy, Swadipta Bose, Saptasree Nair, Aruna N. Sreenivasan, Sreeprasad Shutthanandan, Vaithiyalingam Ramana, Chintalapalle V. |
author_facet | Mallesham, Bandi Roy, Swadipta Bose, Saptasree Nair, Aruna N. Sreenivasan, Sreeprasad Shutthanandan, Vaithiyalingam Ramana, Chintalapalle V. |
author_sort | Mallesham, Bandi |
collection | PubMed |
description | [Image: see text] This work for the first time unfurls the fundamental mechanisms and sets the stage for an approach to derive electrocatalytic activity, which is otherwise not possible, in a traditionally known wide band-gap oxide material. Specifically, we report on the tunable optical properties, in terms of wide spectral selectivity and red-shifted band gap, and electrocatalytic behavior of iron (Fe)-doped gallium oxide (β-Ga(2)O(3)) model system. X-ray diffraction (XRD) studies of sintered Ga(2–x)Fe(x)O(3) (GFO) (0.0 ≤ x ≤ 0.3) compounds provide evidence for the Fe(3+) substitution at Ga(3+) site without any secondary phase formation. Rietveld refinement of XRD patterns reveals that the GFO compounds crystallize in monoclinic crystal symmetry with a C2/m space group. The electronic structure of the GFO compounds probed using X-ray photoelectron spectroscopy data reveals that at lower concentrations, Fe exhibits mixed chemical valence states (Fe(3+), Fe(2+)), whereas single chemical valence state (Fe(3+)) is evident for higher Fe content (x = 0.20–0.30). The optical absorption spectra reveal a significant red shift in the optical band gap with Fe doping. The origin of the significant red shift even at low concentrations of Fe (x = 0.05) is attributed to the strong sp–d exchange interaction originated from the 3d(5) electrons of Fe(3+). The optical absorption edge observed at ≈450 nm with lower intensity is the characteristic of Fe-doped compounds associated with Fe(3+)–Fe(3+) double-excitation process. Coupled with an optical band-gap red shift, electrocatalytic studies of GFO compounds reveal that, interestingly, Fe-doped Ga(2)O(3) compound exhibits electrocatalytic activity in contrast to intrinsic Ga(2)O(3). Fe-doped samples (GFO) demonstrated appreciable electrocatalytic activity toward the generation of H(2) through electrocatalytic water splitting. An onset potential and Tafel slope of GFO compounds include ∼900 mV, ∼210 mV dec(–1) (x = 0.15) and ∼1036 mV, ∼290 mV dec(–1) (x = 0.30), respectively. The electrocatalytic activity of Fe-doped Ga-oxide compounds is attributed to the cumulative effect of different mechanisms such as doping resulting in new catalytic centers, enhanced conductivity, and electron mobility. Hence, in this report, for the first time, we explored a new pathway; the electrocatalytic behavior of Fe-doped Ga(2)O(3) resulted due to Fe chemical states and red shift in the optical band gap. The implications derived from this work may be applicable to a large class of compounds, and further options may be available to design functional materials for electrocatalytic energy production. |
format | Online Article Text |
id | pubmed-6963903 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-69639032020-01-17 Crystal Chemistry, Band-Gap Red Shift, and Electrocatalytic Activity of Iron-Doped Gallium Oxide Ceramics Mallesham, Bandi Roy, Swadipta Bose, Saptasree Nair, Aruna N. Sreenivasan, Sreeprasad Shutthanandan, Vaithiyalingam Ramana, Chintalapalle V. ACS Omega [Image: see text] This work for the first time unfurls the fundamental mechanisms and sets the stage for an approach to derive electrocatalytic activity, which is otherwise not possible, in a traditionally known wide band-gap oxide material. Specifically, we report on the tunable optical properties, in terms of wide spectral selectivity and red-shifted band gap, and electrocatalytic behavior of iron (Fe)-doped gallium oxide (β-Ga(2)O(3)) model system. X-ray diffraction (XRD) studies of sintered Ga(2–x)Fe(x)O(3) (GFO) (0.0 ≤ x ≤ 0.3) compounds provide evidence for the Fe(3+) substitution at Ga(3+) site without any secondary phase formation. Rietveld refinement of XRD patterns reveals that the GFO compounds crystallize in monoclinic crystal symmetry with a C2/m space group. The electronic structure of the GFO compounds probed using X-ray photoelectron spectroscopy data reveals that at lower concentrations, Fe exhibits mixed chemical valence states (Fe(3+), Fe(2+)), whereas single chemical valence state (Fe(3+)) is evident for higher Fe content (x = 0.20–0.30). The optical absorption spectra reveal a significant red shift in the optical band gap with Fe doping. The origin of the significant red shift even at low concentrations of Fe (x = 0.05) is attributed to the strong sp–d exchange interaction originated from the 3d(5) electrons of Fe(3+). The optical absorption edge observed at ≈450 nm with lower intensity is the characteristic of Fe-doped compounds associated with Fe(3+)–Fe(3+) double-excitation process. Coupled with an optical band-gap red shift, electrocatalytic studies of GFO compounds reveal that, interestingly, Fe-doped Ga(2)O(3) compound exhibits electrocatalytic activity in contrast to intrinsic Ga(2)O(3). Fe-doped samples (GFO) demonstrated appreciable electrocatalytic activity toward the generation of H(2) through electrocatalytic water splitting. An onset potential and Tafel slope of GFO compounds include ∼900 mV, ∼210 mV dec(–1) (x = 0.15) and ∼1036 mV, ∼290 mV dec(–1) (x = 0.30), respectively. The electrocatalytic activity of Fe-doped Ga-oxide compounds is attributed to the cumulative effect of different mechanisms such as doping resulting in new catalytic centers, enhanced conductivity, and electron mobility. Hence, in this report, for the first time, we explored a new pathway; the electrocatalytic behavior of Fe-doped Ga(2)O(3) resulted due to Fe chemical states and red shift in the optical band gap. The implications derived from this work may be applicable to a large class of compounds, and further options may be available to design functional materials for electrocatalytic energy production. American Chemical Society 2019-12-27 /pmc/articles/PMC6963903/ /pubmed/31956757 http://dx.doi.org/10.1021/acsomega.9b01604 Text en Copyright © 2019 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Mallesham, Bandi Roy, Swadipta Bose, Saptasree Nair, Aruna N. Sreenivasan, Sreeprasad Shutthanandan, Vaithiyalingam Ramana, Chintalapalle V. Crystal Chemistry, Band-Gap Red Shift, and Electrocatalytic Activity of Iron-Doped Gallium Oxide Ceramics |
title | Crystal Chemistry,
Band-Gap Red Shift, and Electrocatalytic
Activity of Iron-Doped Gallium Oxide Ceramics |
title_full | Crystal Chemistry,
Band-Gap Red Shift, and Electrocatalytic
Activity of Iron-Doped Gallium Oxide Ceramics |
title_fullStr | Crystal Chemistry,
Band-Gap Red Shift, and Electrocatalytic
Activity of Iron-Doped Gallium Oxide Ceramics |
title_full_unstemmed | Crystal Chemistry,
Band-Gap Red Shift, and Electrocatalytic
Activity of Iron-Doped Gallium Oxide Ceramics |
title_short | Crystal Chemistry,
Band-Gap Red Shift, and Electrocatalytic
Activity of Iron-Doped Gallium Oxide Ceramics |
title_sort | crystal chemistry,
band-gap red shift, and electrocatalytic
activity of iron-doped gallium oxide ceramics |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6963903/ https://www.ncbi.nlm.nih.gov/pubmed/31956757 http://dx.doi.org/10.1021/acsomega.9b01604 |
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