Wu, Xiaofeng (2024)
Ternary Bismuth-based Functional Materials for Photoelectrochemical Water Oxidation.
Technische Universität Darmstadt
doi: 10.26083/tuprints-00028052
Dissertation, Erstveröffentlichung, Verlagsversion
Kurzbeschreibung (Abstract)
Ternary bismuth-based oxides are regarded as promising photoanode materials in the field of photoelectrochemical water splitting due to their tunable structure and suitable energy band position. However, an in-depth understanding of bulk defects in structure-activity relationships and interfacial charge transfer kinetics is still lacking but needed for designing optimally functioning photoelectrodes. In the present work, the impact of bulk oxygen vacancies (OVs) in BiOCl and the related induced shallow and deep defect states on the photocurrent was investigated. The results demonstrated that shallow defect states acting as electrons sinks can effectively accelerate separation of charge carriers and remarkably enhance the photocurrent, while deep lying surface states act as recombination centers and are detrimental to photocurrent. Apart from BiOCl, the influence of Mo doping in BiVO_4 on photocurrent, photovoltage, and charge carrier dynamics was investigated. The results showed that both dark- and photocurrent densities of BiVO_4 in OER are dominantly limited by interfacial charge carrier resistance (R_{ct}) rather than bulk resistance (R_{bulk}). This conclusion confirms that the increase of bulk charge carrier concentration is not a decisive factor for improved OER performance of BiVO_4, which is consistent with the viewpoint that photocurrent of BiVO_4 is limited by surface recombination. Based on the BiVO_4 results, we further proposed a semiconductor-electrolyte interface model, in which the surface accumulated hole density in BiVO_4 and Mo-doped BiVO_4 samples during water oxidation can be acquired via employing illumination-dependent Mott-Schottky measurements. According to this model, we demonstrate that the hole transfer rate remains linearly proportional to surface hole density on a log-log scale. Both water oxidation on BiVO_4 and Mo-doped BiVO_4 follow first-order reaction kinetics at low surface hole densities, which is in good agreement with literature. Besides, we find that water oxidation active sites in both BiVO_4 and Mo doped BiVO_4 are very likely to be Bi^{5+}, which are produced by photoexcited or/and electro-induced surface holes, rather than VO_x species or Mo^{6+} due to their insufficient redox potential for water oxidation. Our model gives a relatively complete physical image for generation and transfer of the photo(electro)-induced holes, as well as their accumulation and distribution within the space charge region (SCR) of semiconductors and surface hole-related water oxidation kinetics.
Typ des Eintrags: | Dissertation | ||||
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Erschienen: | 2024 | ||||
Autor(en): | Wu, Xiaofeng | ||||
Art des Eintrags: | Erstveröffentlichung | ||||
Titel: | Ternary Bismuth-based Functional Materials for Photoelectrochemical Water Oxidation | ||||
Sprache: | Englisch | ||||
Referenten: | Hofmann, Prof. Dr. Jan Philipp ; Oropeza Palacio, Dr. Freddy E. | ||||
Publikationsjahr: | 20 September 2024 | ||||
Ort: | Darmstadt | ||||
Kollation: | XIX, 147 Seiten | ||||
Datum der mündlichen Prüfung: | 30 Juli 2024 | ||||
DOI: | 10.26083/tuprints-00028052 | ||||
URL / URN: | https://tuprints.ulb.tu-darmstadt.de/28052 | ||||
Kurzbeschreibung (Abstract): | Ternary bismuth-based oxides are regarded as promising photoanode materials in the field of photoelectrochemical water splitting due to their tunable structure and suitable energy band position. However, an in-depth understanding of bulk defects in structure-activity relationships and interfacial charge transfer kinetics is still lacking but needed for designing optimally functioning photoelectrodes. In the present work, the impact of bulk oxygen vacancies (OVs) in BiOCl and the related induced shallow and deep defect states on the photocurrent was investigated. The results demonstrated that shallow defect states acting as electrons sinks can effectively accelerate separation of charge carriers and remarkably enhance the photocurrent, while deep lying surface states act as recombination centers and are detrimental to photocurrent. Apart from BiOCl, the influence of Mo doping in BiVO_4 on photocurrent, photovoltage, and charge carrier dynamics was investigated. The results showed that both dark- and photocurrent densities of BiVO_4 in OER are dominantly limited by interfacial charge carrier resistance (R_{ct}) rather than bulk resistance (R_{bulk}). This conclusion confirms that the increase of bulk charge carrier concentration is not a decisive factor for improved OER performance of BiVO_4, which is consistent with the viewpoint that photocurrent of BiVO_4 is limited by surface recombination. Based on the BiVO_4 results, we further proposed a semiconductor-electrolyte interface model, in which the surface accumulated hole density in BiVO_4 and Mo-doped BiVO_4 samples during water oxidation can be acquired via employing illumination-dependent Mott-Schottky measurements. According to this model, we demonstrate that the hole transfer rate remains linearly proportional to surface hole density on a log-log scale. Both water oxidation on BiVO_4 and Mo-doped BiVO_4 follow first-order reaction kinetics at low surface hole densities, which is in good agreement with literature. Besides, we find that water oxidation active sites in both BiVO_4 and Mo doped BiVO_4 are very likely to be Bi^{5+}, which are produced by photoexcited or/and electro-induced surface holes, rather than VO_x species or Mo^{6+} due to their insufficient redox potential for water oxidation. Our model gives a relatively complete physical image for generation and transfer of the photo(electro)-induced holes, as well as their accumulation and distribution within the space charge region (SCR) of semiconductors and surface hole-related water oxidation kinetics. |
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Status: | Verlagsversion | ||||
URN: | urn:nbn:de:tuda-tuprints-280520 | ||||
Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie | ||||
Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Fachgebiet Oberflächenforschung |
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Hinterlegungsdatum: | 20 Sep 2024 12:10 | ||||
Letzte Änderung: | 24 Sep 2024 11:54 | ||||
PPN: | |||||
Referenten: | Hofmann, Prof. Dr. Jan Philipp ; Oropeza Palacio, Dr. Freddy E. | ||||
Datum der mündlichen Prüfung / Verteidigung / mdl. Prüfung: | 30 Juli 2024 | ||||
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