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Electronically-Coupled Phase Boundaries in α‑Fe2O3/Fe3O4 Nanocomposite Photoanodes for Enhanced Water Oxidation
University of Cologne, Institute of Inorganic Chemistry, University of Cologne, 50939, Cologne, Germany.
University of Cologne, Institute of Inorganic Chemistry, University of Cologne, 50939, Cologne, Germany.
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science.ORCID iD: 0000-0002-7893-7405
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Material Science.ORCID iD: 0000-0001-7475-6394
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2019 (English)In: ACS APPLIED NANO MATERIALS, E-ISSN 2574-0970, Vol. 2, no 1, p. 334-342Article in journal (Refereed) Published
Abstract [en]

Photoelectrochemical (PEC) water splittingreactions are promising for sustainable hydrogen productionfrom renewable sources. We report here, the preparation of α-Fe2O3/Fe3O4 composite films via a single-step chemical vapordeposition of [Fe(OtBu)3]2 and their use as efficient photoanode materials in PEC setups. Film thickness and phase segregation was controlled by varying the deposition time and corroborated through cross-section Raman spectroscopy and scanning electron microscopy. The highest water oxidationactivity (0.48 mA/cm2 at 1.23 V vs RHE) using intermittent AM 1.5 G (100 mW/cm2) standard illumination was found forhybrid films with a thickness of 11 μm. This phenomenon is attributed to an improved electron transport resulting from ahigher magnetite content toward the substrate interface and an increased light absorption due to the hematite layer mainly located at the top surface of the film. The observed high efficiency of α-Fe2O3/Fe3O4 nanocomposite photoanodes is attributed to the close proximity and establishment of 3D interfaces between the weakly ferro- (Fe2O3) and ferrimagnetic (Fe3O4) oxides, which in view of their differential chemical constitution andvalence states of Fe ions (Fe2+/Fe3+) can enhance the charge separation and thus the overall electrical conductivity of the layer.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019. Vol. 2, no 1, p. 334-342
Keywords [en]
solar water splitting, valence dynamics, magnetite, Raman, single-source CVD, heterostructures
National Category
Composite Science and Engineering Chemical Engineering
Research subject
Experimental Physics; Chemical Technology
Identifiers
URN: urn:nbn:se:ltu:diva-73139DOI: 10.1021/acsanm.8b01936ISI: 000464491500036Scopus ID: 2-s2.0-85065245957OAI: oai:DiVA.org:ltu-73139DiVA, id: diva2:1294688
Note

Validerad;2019;Nivå 2;2019-03-13 (oliekm)

Available from: 2019-03-08 Created: 2019-03-08 Last updated: 2025-02-18Bibliographically approved
In thesis
1. Advanced Nanostructured Transition Metal Oxide Semiconductors for Solar Energy Applications
Open this publication in new window or tab >>Advanced Nanostructured Transition Metal Oxide Semiconductors for Solar Energy Applications
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Avanceradenanostrukturerade halvledare av övergångsmetalloxid för solenergiapplikationer
Abstract [en]

Increasing energy consumption and its environmental impacts make it necessary to look for alternative energy sources. Solar energy as huge energy source that can cover the terms sustainability is considered as a favorable alternative. Optoelectronic devices like solar cells and photoelectrochemical cells are in very high interest to provide the energy that we need. They can convert solar energy, as a sustainable energy source, to electricity and fuel. Transition metal oxides (TMOs) due to high chemical stability, abundance, facile production and low cost are favorable materials to be used in these optoelectronic applications. In TMOs, d orbitals electrons contribute in forming bonds that gives special magnetic, electronic and geometric characteristics to these materials. They can be synthesized with different types of chemical and physical deposition methods.

The electronic properties of TMOs varies from metallic characteristics to electrical insulators. Transition metal oxide semiconductors (TMOSs) are mostly used in optoelectronic devices. Tuning the properties of TMOSs like, composition, morphology, dimensions, crystal structure, improves the performance of the optoelectronic devices. The light absorption, charge carrier mobility, the time scale between charge injection, regeneration and recombination processes are some of the properties critical to exploitation of TMOSs in solar cells and solar fuel technology.

In this thesis, we explore the use of nanostructured TMOSs in all-oxide solar cells, photodetectors and photoelectrochemical cells. 1-dimentional heterojunctions of n-type transparent semi-conductive metal oxides (ZnO and TiO2) in conjunction to p-type light absorbing semi-conductive metal oxides (Cu2O and Co3O4) have been tested in all-oxide photodetectors and solar cells.  It is shown that the 1-dimentional nanostructured geometry (nanowires, nanotubes) improves the charge separation and charge transport properties. Increasing the surface to volume aspect ratio in nanowires and nanotubes improves the light absorption compare to the thin film geometry. Our ZnO-Cu2O core-shell nanowire photodetector is the fastest visible light photodetector reported till now. Mesoporous NiO photocathode, sensitized with a biomimetic FeFe-catalyst and coumarin C343 dye, was tested in a photoelectrochemical cell for hydrogen production. This system is the first solar fuel device based on a biomimetic FeFe-catalyst and it shows a Faradic efficiency of 50% in hydrogen production. Cobalt catalysts have higher Faradic efficiency but their performance due to hydrolysis in low pH condition is limited. Nanostructured hematite/magnetite film as a photoanode was tested in a photoelectrochemical cell for water splitting. This hybrid electrode improved the photoactivity of the photoelectrochemical cell for water splitting. The main mechanism for the improvement of the functional properties relies with the role of the magnetite phase, which improves the charge carrier mobility of the composite system, compared to pure hematite, which acts as good light absorbing semiconductor.

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2019
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
Keywords
Metal Oxide, Photovoltaic, Semiconductors, Self-powered photodetectors, Photoelectrochemical cell, Solar fuel, Water splitting
National Category
Materials Engineering
Research subject
Experimental Physics
Identifiers
urn:nbn:se:ltu:diva-73709 (URN)978-91-7790-366-6 (ISBN)978-91-7790-367-3 (ISBN)
Public defence
2019-06-14, E632, Luleå University of Technology, Luleå, 10:00 (English)
Opponent
Supervisors
Funder
Vinnova, 224320
Available from: 2019-04-23 Created: 2019-04-19 Last updated: 2023-09-05Bibliographically approved

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Ghamgosar, PedramYou, ShujieMouzon, JohanneVomiero, Alberto

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