Logo: to the web site of Uppsala University

uu.sePublications from Uppsala University
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Defect induced Raman scattering in Cu2O Nanopillars and Their Performance for Photocatalytic Water Purification
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.ORCID iD: 0000-0002-0069-8707
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: 0000-0003-2759-7356
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Polluted water is a severe problem in many parts of the world and is expected to cause stress in water systems in developed countries with an increased use of chemicals and rising urban densification. Advanced oxidation processes (AOPs) using photogenerated charges in semiconductors constitute an approach to reduce and oxidize pollutants, with an efficiency that, in turn, depend on the photo physics and defect chemistry of the photocatalyst. The use of visible-light-active nanostructures for AOPs is attractive, because they can offer viable opportunities for water purification by using a large part of the solar spectrum and providing intrinsically larger surface areas. Here, 3D nanostructured copper pillars are investigated together with their thin Cu2O coating created via low-temperature oxidation in air and compared with corresponding flat surfaces. The formed copper oxide is analysed with X-ray diffraction, scanning electron microscopy (SEM) and Raman spectroscopy. Defect induced Raman scattering is analysed and corroborated by theoretical Raman spectra using linear response density functional theory (DFT) calculations for full vibrational mode analysis, revealing activation of several vibrational modes that are otherwise inactive in pristine Cu2O. The more specific effect of different vacancies for the activation of different modes, is reviewed and analysed in more detail. The thickest surface oxide layers on the 3D structures show outgrowth of CuO nano-needles rationalized through a copper ion diffusion mechanism. All of the Cu-supported copper oxide systems exhibit effective photocatalytic performance with 3D nanopillar structures further increasing the efficiency by 34% compared to their planar counterpart.

Keywords [en]
Cu2O, Defect induced Raman scatterin, Electrodeposition, thredimensional structures, Photocatalytic water purification
National Category
Materials Engineering
Research subject
Engineering Science with specialization in Solid State Physics; Chemistry with specialization in Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-486412OAI: oai:DiVA.org:uu-486412DiVA, id: diva2:1701792
Funder
Swedish Research Council Formas, 2016-00908Swedish Research Council, 2019-00207Available from: 2022-10-07 Created: 2022-10-07 Last updated: 2022-10-15
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

Open Access in DiVA

No full text in DiVA

Authority records

Valvo, MarioThyr, JakobEdvinsson, Tomas

Search in DiVA

By author/editor
Valvo, MarioThyr, JakobEdvinsson, Tomas
By organisation
Department of Chemistry - ÅngströmSolid State Physics
Materials Engineering

Search outside of DiVA

GoogleGoogle Scholar

urn-nbn

Altmetric score

urn-nbn
Total: 129 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf