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Optical Quantum Confinement in Ultrasmall ZnO and the Effect of Size on Their Photocatalytic Activity
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0001-6717-0408
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solid State Physics.ORCID iD: 0000-0003-2759-7356
2020 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 124, no 11, p. 6395-6404Article in journal (Refereed) Published
Abstract [en]

Zinc oxide is a well-known metal oxide semiconductor with a wide direct band gap that offers a promising alternative to titanium oxide in photocatalytic applications. ZnO is studied here as quantum dots (QDs) in colloidal suspensions, where ultrasmall nanoparticles of ZnO show optical quantum confinement with a band gap opening for particles below 9 nm in diameter from the shift of the band edge energies. The optical properties of growing ZnO QDs are determined with Tauc analysis, and a system of QDs for the treatment and degradation of distributed threats is analyzed using an organic probe molecule, methylene blue, whose UV/vis spectrum is analyzed in some detail. The effect of optical properties of the QDs and the kinetics of dye degradation are quantified for low-dimensional ZnO materials in the range of 3-8 nm and show a substantial increase in photocatalytic activity compared to larger ZnO particles. This is attributed to a combined effect from the increased surface area as well as a quantum confinement effect that goes beyond the increased surface area. The results show a significantly higher photocatalytic activity for the QDs between 3 and 6 nm with a complete decolorization of the organic probe molecule, while QDs from 6 nm and upward in diameter show signs of competing reduction reactions. Our study shows that ultrasmall ZnO particles have a reactivity beyond that which is expected because of their increased surface area and also demonstrates size-dependent reaction pathways, which introduces the possibility for size-selective catalysis.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2020. Vol. 124, no 11, p. 6395-6404
National Category
Physical Chemistry Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-410900DOI: 10.1021/acs.jpcc.9b11229ISI: 000526396000057OAI: oai:DiVA.org:uu-410900DiVA, id: diva2:1431792
Funder
Swedish Research Council Formas, 2016-00908Available from: 2020-05-25 Created: 2020-05-25 Last updated: 2023-10-30Bibliographically approved
In thesis
1. Nanostructured ZnO and metal chalcogenide films for solar photocatalysis
Open this publication in new window or tab >>Nanostructured ZnO and metal chalcogenide films for solar photocatalysis
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The increasing demand for clean energy and safe water resources has driven the development of efficient and sustainable technologies. Among these technologies, photocatalysis using semiconducting materials has emerged as a promising solution for both solar hydrogen generation and water purification. Low-dimensional ZnO, including nanorods, nanoparticles, and quantum confined particles (so called quantum dots), has demonstrated excellent photocatalytic properties due to their large surface area, high electron mobility, and tunable band gap.

The work in this thesis aims to investigate the potential of low-dimensional ZnO alone and in combination with CdS and Fe2O3 for solar hydrogen generation and photocatalytic water purification. The thesis includes a comprehensive analysis of the synthesis, characterization, and optimization of low-dimensional ZnO-based photocatalyst systems for solar hydrogen generation and photocatalytic water purification. Additionally, the thesis will evaluate the performance of the ZnO-based photocatalysts under different experimental conditions, either as photoelectrodes or as distributed particle systems for water purification. The work includes detailed size control of ZnO by itself in dimensions below 10 nm using a hydrothermal method, to provide an increased total surface area and introduce quantum confinement effects that increase the band gap to enable degradation of chemical bonds in a model pollutant in a distributed system for water purification. The work also includes a relatively detailed study of the phonon–phonon and electron–phonon coupling as a function of dimension from 10 nm to 150 nm for ZnO using non-resonant and resonant Raman spectroscopy. Ultimately, the thesis aims to provide insight into the potential of low-dimensional ZnO alone and in combination with other inorganic materials for solar hydrogen generation and photocatalytic water purification and pave the way for the development of efficient and sustainable technologies for clean energy and safe water resources.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2023. p. 129
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2337
Keywords
photocatalysis, zinc oxide, quantum dots, nanorods, quantum confinement, low-dimensional, cathodic electrodeposition, Raman spectroscopy
National Category
Physical Chemistry Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-515258 (URN)978-91-513-1961-2 (ISBN)
Public defence
2023-12-18, Polhemsalen, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2023-11-24 Created: 2023-10-30 Last updated: 2023-11-24

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Ahmed, TahaEdvinsson, Tomas

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