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Energy Alignment of Quantum-Confined ZnO Particles with Copper Oxides for Heterojunctions with Improved Photocatalytic Performance
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solid State Physics.ORCID iD: 0000-0002-9812-7370
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solid State Physics.ORCID iD: 0000-0003-2917-8569
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solid State Physics.ORCID iD: 0000-0003-0296-5247
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solid State Physics.ORCID iD: 0000-0003-2759-7356
2022 (English)In: ACS Nanoscience Au, E-ISSN 2694-2496, Vol. 2, no 2, p. 128-139Article in journal (Refereed) Published
Abstract [en]

The ability to control electronic states by utilizing quantum confinement of one of the material components in heterojunctions is a promising approach to perform energy-level matching. In this work, we report the possibility to achieve optimum energy alignment in heterojunctions made from size-controlled quantum dots (Q-dots) of ZnO in combination with three copper oxides: Cu2O, Cu4O3, and CuO. Quantum confinement effects on the ZnO nanoparticles in the diameter range 2.6–7.4 nm showed that the direct optical band gap decreased from 3.99 to 3.41 eV, with a dominating shift occurring in the conduction band (CB) edge, and thus the possibility to obtain close to 0.6 eV CB edge shift by controlling the size of ZnO. The effect was utilized to align the electronic bands in the ZnO Q-dot/copper oxide heterojunctions to allow for charge transfer between the materials and to test the ability to improve the photocatalytic performance for the system, evaluated by the transformation of a dye molecule in water. The catalyst materials were investigated by X-ray diffraction, scanning electron microscopy, ultraviolet–visible (UV–vis), photoluminescence, and Raman spectroscopy. The most promising material combination was found to be the Cu2O copper oxide in combination with an energy aligned ZnO Q-dot system with approximately 7 nm diameter, showing strong synergy effects in good agreement with the energy-level analysis, outperforming the added effect of its individual components, ZnO-Q-dots and Cu2O, by about 140%. The results show that utilization of a heterojunction with controllable energy alignment can provide a drastically improved photocatalytic performance. Apart from increased photocatalytic activity, specific surface states of ZnO are quenched when the heterojunction is created. It is anticipated that the same approach can be utilized in several material combinations with the added benefit of a system with controllable overpotential and thus added specificity for the targeted reduction reaction.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2022. Vol. 2, no 2, p. 128-139
Keywords [en]
quantum confinement, ZnO quantum dots, copper oxide, energy alignment, heterojunctions, photocatalysis
National Category
Nano Technology Materials Engineering
Research subject
Engineering Science with specialization in Solid State Physics
Identifiers
URN: urn:nbn:se:uu:diva-479075DOI: 10.1021/acsnanoscienceau.1c00040ISI: 001027129400001PubMedID: 37101663OAI: oai:DiVA.org:uu-479075DiVA, id: diva2:1697624
Funder
Swedish Research Council Formas, 2016-00908Available from: 2022-09-21 Created: 2022-09-21 Last updated: 2023-10-13Bibliographically approved
In thesis
1. Low dimensional Zinc- and Copper Oxides and their Electronic, Vibrational and Photocatalytic Properties
Open this publication in new window or tab >>Low dimensional Zinc- and Copper Oxides and their Electronic, Vibrational and Photocatalytic Properties
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Pollution of water resources is a growing problem in the world and this has drawn the attention to photocatalysis, which is an emerging technology for water purification. In this thesis, low dimensional zinc oxide and copper oxides, which are promising photocatalytic materials, have been studied. In the initial work, an approach for determining the crystal orientation in ZnO nanomaterials was developed based on polarized Raman spectroscopy. The approach was extended to non-polarized Raman spectroscopy for convenient crystal orientation determination. The results were corroborated by density functional theory (DFT) calculations providing a full vibrational mode analysis of ZnO, including higher-order Raman scattering. Photocatalyst materials based on both ZnO and copper oxides were synthesized, starting with visible light absorbing Cu2O prepared by low temperature thermal oxidation of flat and 3D structured Cu-foils. Defect induced Raman scattering revealed Raman activity in modes that are only IR active or optically silent in pristine Cu2O, with mode assignments supported by DFT calculations. Experiment with solar light illuminated Cu2O showed efficient degradation of organic water-soluble molecules and degradation rates could be further increased by 3D structuring into nanopillars. With the aim of creating a combined photocatalyst that use favourable properties from several materials, nanoparticles of ZnO were synthesized and deposited onto Cu2O, Cu4O3 and CuO. ZnO of sufficiently small size exhibit quantum confinement, which allowed for tuning of the electronic and optical properties of ZnO and this was utilized for energy level alignment in heterojunctions with copper oxides. The heterojunctions were shown to facilitate charge transfer which improved the photocatalytic properties of the dual catalysts compared to the single components. The quantum confinement effects in ZnO nanoparticles were further investigated by more detailed electrochemical measurements. The main finding was that quantum confinement results in a large decrease in the available electronic density of states which has clear implications on the capacitance and photon absorption in the material. Raman spectroscopy has been a central tool in all work, and the thesis ends with a study that goes through and explain spurious Raman signals. The contribution shows how to identify and avoid spectral artefacts and other light generating processes that compete with the Raman signal and guide the acquisition of good quality spectra.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2022. p. 103
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2199
Keywords
ZnO, Cu2O, CuO, Cu4O3, Photocatalysis, Raman spectroscopy, Nano materials, Quantum confinement, Quantum dots, Size dependent properties, Crystal orientation, Density functional theory
National Category
Materials Engineering
Research subject
Engineering Science with specialization in Solid State Physics
Identifiers
urn:nbn:se:uu:diva-486457 (URN)978-91-513-1620-8 (ISBN)
Public defence
2022-11-25, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2022-11-01 Created: 2022-10-09 Last updated: 2022-12-12

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Thyr, JakobMontero, JoséÖsterlund, LarsEdvinsson, Tomas

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