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Theoretical investigation of photocatalytic water splitting on surfaces and thin films of perovskite oxynitrides

English title Theoretical investigation of photocatalytic water splitting on surfaces and thin films of perovskite oxynitrides
Applicant Aschauer Ulrich
Number 157615
Funding scheme SNSF Professorships
Research institution Departement für Chemie, Biochemie und Pharmazie Universität Bern
Institution of higher education University of Berne - BE
Main discipline Physical Chemistry
Start/End 01.01.2016 - 31.12.2019
Approved amount 1'426'477.00
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All Disciplines (3)

Discipline
Physical Chemistry
Material Sciences
Condensed Matter Physics

Keywords (5)

Surface Properties; Perovskite; Oxynitride; Density functional theory; Photocatalysis

Lay Summary (German)

Lead
Oxidmaterialien, die in einer Perowskit-Struktur kristallisieren, weisen aufgrund ihrer strukturellen und chemischen Vielfalt ein grosses Potential für Anwendungen im Bereich der erneuerbaren Energien auf. Für die Wasserstoffgewinnung anhand von Wasserspaltung zeigen speziell Perowskit Oxinitride mit einer Kombination aus Sauerstoff- und Stickstoffanionen experimentell höchst vielversprechende Resultate. Deren Oberflächenstruktur und -chemie, welche für dieses verbesserte Verhalten mitverantwortlich sein muss, ist jedoch weitgehend unbekannt. Ein detailliertes Verständnis verlangt eine Erforschung der Oberfläche auf atomarer Ebene, was rein experimentell nur schwer realisierbar ist, durch die Kombination mit theoretischen Berechnungen aber möglich wird. Dieses Wissen ist unbedingt erforderlich um den Wirkungsgrad von Oxinitriden bei der Wasserspaltung weiter zu verbessern oder komplett neue Materialzusammensetzungen mit optimierten Eigenschaften zu entwickeln.
Lay summary

Inhalt und Ziel des Forschungsprojekts

Ziel dieses Forschungsprojekts ist es, mittels quantenmechanischer Berechnungen die grundlegenden Reaktionsmechanismen der Wasserspaltung auf Perowskit Oxinitriden zu untersuchen und deren oberflächenphysikalische und –chemische Eigenschaften mit denen von stickstofffreien Oxiden zu vergleichen. Dazu werden wir in unserer Forschung i) für unterschiedliche Oxinitridverbindungen die Oberflächenstruktur bestimmen. Dies ermöglicht es, ii) den Aufenthaltsort von Lochladungsträgern auf diesen Oberflächen zu untersuchen um schliesslich iii) deren Rolle bei der Wasseroxidation zu ergründen. Ein letztes Ziel unserer Arbeit ist es, iv) den tendenziellen Einfluss der chemischen Zusammensetzung, der Kristallstruktur und externer mechanischer Verspannungen auf den Wirkungsgrad festzustellen, um damit allgemeine Richtlinien zur Entwicklung neuer Materialien und deren Optimierung zu schaffen.

Wissenschaftlicher und gesellschaftlicher Kontext des Forschungsprojekts

Die theoretischen Arbeiten in diesem Projekt werden in enger Zusammenarbeit mit experimentellen Partnern durchgeführt, was den Transfers des erlangten Grundlagenwissens in die angewandte Wissenschaft und schlussendlich in die Industrie sicherstellt. Es resultieren innovative Materialen, welche aus Sonnenlicht und Wasser effizient Wasserstoffgas erzeugen. Letzteres gilt als vielversprechender Brennstoff zukünftiger Motoren, dessen umweltfreundliche Erzeugung eine Notwendigkeit für dieses alternative Antriebskonzept darstellt. Mit der absehbaren Knappheit fossiler Brennstoffe und deren schädlichen Effekt auf die Umwelt benötigt unsere Gesellschaft dringend erneuerbare und umweltneutrale Energieträger, um die allgemeine Mobilität und Gesundheit zukünftiger Generationen zu garantieren.

Direct link to Lay Summary Last update: 12.11.2015

Responsible applicant and co-applicants

Employees

Publications

Publication
Catalysis on oxidized ferroelectric surfaces—Epitaxially strained LaTiO2N and BaTiO3 for photocatalytic water splitting
Vonrüti Nathalie, Aschauer Ulrich (2020), Catalysis on oxidized ferroelectric surfaces—Epitaxially strained LaTiO2N and BaTiO3 for photocatalytic water splitting, in The Journal of Chemical Physics, 152(2), 024701-024701.
Cation Ordering and Redox Chemistry of Layered Ni-Rich LixNi1–2yCoyMnyO2: An Operando Raman Spectroscopy Study
Flores Eibar, Novák Petr, Aschauer Ulrich, Berg Erik J. (2019), Cation Ordering and Redox Chemistry of Layered Ni-Rich LixNi1–2yCoyMnyO2: An Operando Raman Spectroscopy Study, in Chemistry of Materials, 32(1), 186-194.
Suitability of Different Sr2TaO3N Surface Orientations for Photocatalytic Water Oxidation
Bouri Maria, Aschauer Ulrich (2019), Suitability of Different Sr2TaO3N Surface Orientations for Photocatalytic Water Oxidation, in Chemistry of Materials, 32(1), 75-84.
The role of metastability in enhancing water-oxidation activity
Vonrüti Nathalie, Aschauer Ulrich (2019), The role of metastability in enhancing water-oxidation activity, in Physical Chemistry Chemical Physics, 21(44), 24354-24360.
Water oxidation catalysis on reconstructed NaTaO3 (001) surfaces
Ouhbi Hassan, Aschauer Ulrich (2019), Water oxidation catalysis on reconstructed NaTaO3 (001) surfaces, in Journal of Materials Chemistry A, 7(28), 16770-16776.
Band-gap engineering in AB(OxS1−x)3 perovskite oxysulfides: a route to strongly polar materials for photocatalytic water splitting
Vonrüti Nathalie, Aschauer Ulrich (2019), Band-gap engineering in AB(OxS1−x)3 perovskite oxysulfides: a route to strongly polar materials for photocatalytic water splitting, in Journal of Materials Chemistry A, 7(26), 15741-15748.
Nitrogen Loss and Oxygen Evolution Reaction Activity of Perovskite Oxynitrides
Ouhbi Hassan, Aschauer Ulrich (2019), Nitrogen Loss and Oxygen Evolution Reaction Activity of Perovskite Oxynitrides, in ACS Materials Letters, 1(1), 52-57.
Examining the Structure Sensitivity of the Oxygen Evolution Reaction on Pt Single‐Crystal Electrodes: A Combined Experimental and Theoretical Study
Bizzotto Francesco, Ouhbi Hassan, Fu Yongchun, Wiberg Gustav K. H., Aschauer Ulrich, Arenz Matthias (2019), Examining the Structure Sensitivity of the Oxygen Evolution Reaction on Pt Single‐Crystal Electrodes: A Combined Experimental and Theoretical Study, in ChemPhysChem, 20(22), 3154-3162.
Water-Induced Reversal of the TiO2 (011)-(2×1) Surface Reconstruction: Observed with in Situ Surface X-ray Diffraction
Hussain Hadeel, Ahmed Mahmoud H. M., Torrelles Xavier, Grinter David C., Cabailh Gregory, Bikondoa Oier, Nicklin Christopher, Aschauer Ulrich, Lindsay Robert, Thornton Geoff (2019), Water-Induced Reversal of the TiO2 (011)-(2×1) Surface Reconstruction: Observed with in Situ Surface X-ray Diffraction, in The Journal of Physical Chemistry C, 123(22), 13545-13550.
Anion-order driven polar interfaces at LaTiO2N surfaces
Ninova Silviya, Aschauer Ulrich (2019), Anion-order driven polar interfaces at LaTiO2N surfaces, in Journal of Materials Chemistry A, 7(5), 2129-2134.
Synthesis and Size-Dependent Optical Properties of Intermediate Band Gap Cu3VS4 Nanocrystals
Mantella Valeria, Ninova Silviya, Saris Seryio, Loiudice Anna, Aschauer Ulrich, Buonsanti Raffaella (2018), Synthesis and Size-Dependent Optical Properties of Intermediate Band Gap Cu3VS4 Nanocrystals, in Chemistry of Materials, 31(2), 532-540.
Elucidation of LixNi0.8Co0.15Al0.05O2 Redox Chemistry by Operando Raman Spectroscopy
Flores Eibar, Vonrüti Nathalie, Novák Petr, Aschauer Ulrich, Berg Erik J. (2018), Elucidation of LixNi0.8Co0.15Al0.05O2 Redox Chemistry by Operando Raman Spectroscopy, in Chemistry of Materials, 30(14), 4694-4703.
Surface and Defect Chemistry of Oxide Materials
Aschauer Ulrich (2018), Surface and Defect Chemistry of Oxide Materials, in CHIMIA International Journal for Chemistry, 72(5), 286-290.
Anion Order and Spontaneous Polarization in LaTiO2N Oxynitride Thin Films
Vonrüti Nathalie, Aschauer Ulrich (2018), Anion Order and Spontaneous Polarization in LaTiO2N Oxynitride Thin Films, in Physical Review Letters, 120(4), 046001-046001.
Bulk and surface properties of the Ruddlesden–Popper oxynitride Sr2TaO3N
Bouri Maria, Aschauer Ulrich (2018), Bulk and surface properties of the Ruddlesden–Popper oxynitride Sr2TaO3N, in Physical Chemistry Chemical Physics, 20(4), 2771-2776.
Surface Structure of TiO2 Rutile (011) Exposed to Liquid Water
Balajka Jan, Aschauer Ulrich, Mertens Stijn F. L., Selloni Annabella, Schmid Michael, Diebold Ulrike (2017), Surface Structure of TiO2 Rutile (011) Exposed to Liquid Water, in The Journal of Physical Chemistry C, 121(47), 26424-26431.
Protein Corona: Impact of Lymph Versus Blood in a Complex In Vitro Environment
Bonvin Debora, Aschauer Ulrich, Alexander Duncan T. L., Chiappe Diego, Moniatte Marc, Hofmann Heinrich, Mionić Ebersold Marijana (2017), Protein Corona: Impact of Lymph Versus Blood in a Complex In Vitro Environment, in Small, 13(29), 1700409-1700409.
LaTiOxNy Thin Film Model Systems for Photocatalytic Water Splitting: Physicochemical Evolution of the Solid-Liquid Interface and the Role of the Crystallographic Orientation
Pichler Markus, Si Wenping, Haydous Fatima, Téllez Helena, Druce John, Fabbri Emiliana, Kazzi Mario El, Döbeli Max, Ninova Silviya, Aschauer Ulrich, Wokaun Alexander, Pergolesi Daniele, Lippert Thomas (2017), LaTiOxNy Thin Film Model Systems for Photocatalytic Water Splitting: Physicochemical Evolution of the Solid-Liquid Interface and the Role of the Crystallographic Orientation, in Advanced Functional Materials, 27(20), 1605690-1605690.
Synthesis of Responsive Two-Dimensional Polymers via Self-Assembled DNA Networks
Yu Hao, Alexander Duncan T. L., Aschauer Ulrich, Häner Robert (2017), Synthesis of Responsive Two-Dimensional Polymers via Self-Assembled DNA Networks, in Angewandte Chemie International Edition, 56(18), 5040-5044.
Surface structure and anion order of the oxynitride LaTiO2N
Ninova Silviya, Aschauer Ulrich (2017), Surface structure and anion order of the oxynitride LaTiO2N, in Journal of Materials Chemistry A, 5(22), 11040-11046.
Low-Dimensional Tin(II) Iodide Perovskite Structures Templated by an Aromatic Heterocyclic Cation
Liu Xunshan, Chen Songjie, Hauser Jürg, Laukhin Vladimir, Decurtins Silvio, Aschauer Ulrich, Liu Shi-Xia (2016), Low-Dimensional Tin(II) Iodide Perovskite Structures Templated by an Aromatic Heterocyclic Cation, in Crystal Growth & Design, 16(9), 5230-5237.

Collaboration

Group / person Country
Types of collaboration
Thomas Lippert, PSI Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Ulrike Diebold, TU Vienna Austria (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Tetsuya HASEGAWA Japan (Asia)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Simone Pokrant, University of Salzburg, formerly EMPA & HTW Saar Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
molCH Meeting 2019 Talk given at a conference Surface structure and reactivity of
perovskite oxynitrides 21.06.2019 Bern, Switzerland Aschauer Ulrich;
E-MRS Spring Meeting 2019 Talk given at a conference Strategies to combine small band gaps and ferroelectricity for photocatalytic water-splitting with mixed anion perovskites 27.05.2019 Nice, France Aschauer Ulrich; Vonrüti Nathalie;
E-MRS Spring Meeting 2019 Talk given at a conference Photocatalytical activity of Sr2TaO3N bulk and surfaces by density functional theory 27.05.2019 Nice, France Aschauer Ulrich; Bouri Maria;
E-MRS Spring Meeting 2019 Talk given at a conference Catalytic and interface functionality by anion order in oxynitrides 27.05.2019 Nice, France Aschauer Ulrich; Ninova Silviya;
Universität Salzburg, Chemistry and Physics of Materials Seminar Individual talk Surface structure and reactivity of
perovskite oxynitrides 15.05.2019 Salzburg, Austria Aschauer Ulrich;
MRS Spring Meeting 2019 Talk given at a conference The Role of Catalyst Metastability in Enhancing the Oxygen Evolution Reaction 22.04.2019 Phoenix, United States of America Aschauer Ulrich; Vonrüti Nathalie;
Uni Zürich Seminar in Solid-State Physics Individual talk Pressure and biaxial strain dependent properties of perovskite oxides and derived mixed-anion materials 17.04.2019 Zürich, Switzerland Aschauer Ulrich;
APS March Meeting 2019 Talk given at a conference Strain-induced heteronuclear charge disproportionation in EuMnO3 04.03.2019 Boston, United States of America Aschauer Ulrich; Vonrüti Nathalie;
APS March Meeting 2019 Talk given at a conference Ferroelectric Materials for Photocatalytic Water-Splitting:Strained Mixed Anion Perovskites 04.03.2019 Boston, United States of America Aschauer Ulrich; Vonrüti Nathalie;
SAOG Meeting 2019 Poster Oxygen Evolution Reaction on b-Mn2V2O7 and b-Cu2V2O7 31.01.2019 Fribourg, Switzerland Aschauer Ulrich; Ninova Silviya;
Swiss Chemical Society Fall Meeting 2018 Poster Bulk and surface properties of Sr2TaO3N by density functional theory 07.09.2018 Lausanne, Switzerland Aschauer Ulrich; Bouri Maria;
E-MRS Spring Meeting Talk given at a conference Structural and electronic properties of Sr2TaO3N bulk and surfaces by density functional theory 18.06.2018 Strasbourg , France Aschauer Ulrich; Bouri Maria;
E-MRS Spring Meeting Talk given at a conference Effect of anion order and spontaneous polarisation on bandgaps in epitaxially strained oxynitrides 18.06.2018 Strasbourg , France Vonrüti Nathalie; Aschauer Ulrich;
Swiss Academy of Science Young Faculty Meeting Talk given at a conference Surface and defect chemistry of oxide and oxynitride materials 05.06.2018 Bern, Switzerland Aschauer Ulrich;
34th SAOG Meeting Poster Bulk and surface properties of Sr2TaO3N by density functional theory calculations 01.02.2018 Fribourg, Switzerland Aschauer Ulrich; Bouri Maria;
34th SAOG Meeting Poster Polarisation of oxidized ferroelectric surfaces using density functional theory: The case of BaTiO3 01.02.2018 Fribourg, Switzerland Vonrüti Nathalie; Aschauer Ulrich;
Swiss Chemical Society Fall Meeting 2017 Poster DFT Study on the LaTiO2N Surface Chemical Composition and Orientation 21.08.2017 Bern, Switzerland Aschauer Ulrich; Ninova Silviya;
Swiss Chemical Society Fall Meeting 2017 Talk given at a conference Surface structure and reactivity of perovskite oxynitride materials 21.08.2017 Bern, Switzerland Aschauer Ulrich;
Swiss Chemical Society Fall Meeting 2017 Poster Bulk and surface properties of Sr2TaO3N by density functional theory calculations 21.08.2016 Bern, Switzerland Aschauer Ulrich; Bouri Maria;


Self-organised

Title Date Place
MRS Fall Meeting 2017 26.11.2017 Boston, United States of America

Communication with the public

Communication Title Media Place Year
Talks/events/exhibitions Biochemie am Samstag German-speaking Switzerland 2017
Talks/events/exhibitions Nacht der Forschung, Universität Bern German-speaking Switzerland 2017

Associated projects

Number Title Start Funding scheme
187185 Theoretical investigation of photocatalytic water splitting on surfaces and thin films of perovskite oxynitrides 01.01.2020 SNSF Professorships

Abstract

This project will establish, by means of first-principles theoretical calculations, the fundamental reaction mechanisms for photocatalytic H2 production by water splitting on perovskite oxynitride photo-electrode materials. Perovskite oxynitrides exhibits some of the highest H2 and O2 evolution rates and are promising candidates for the next generation of water-splitting photocatalysis. The superior photocatalytic activity of these materials relative to pure oxides has so far been explained in terms of differences in their bulk electronic structure. This project will for the first time investigate the surface physico-chemical differences between oxides and oxynitrides and their effect on water splitting. Starting from materials known to split water under light irradiation, we will study the effect of the chemical composition to derive general trends for the photocatalytic reactivity. Furthermore we will investigate the role of defects on the reactivity of such surfaces as well as the epitaxial-strain control of the electronic structure and the defect profile to model the situation occurring in thin films and heterostructures.The planned work is entirely new, as perovskite oxynitride surfaces have never been computationally investigated, even though these materials are amongst the most promising photocatalytic water splitters. Without the fundamental mechanistic knowledge that this project will generate, a targeted improvement of these materials towards higher H2 evolution is impossible.The planned collaboration with state-of-the-art experiment will be of mutual benefit for validation and interpretation of results and will ensure publications at the highest level. The proposed research integrates well with the strategic reorientation into energy-related research at the Department of Chemistry and Biochemistry of the University of Bern as well as on a national level with the recently established Competence Centers for Energy Research (SCCER) and the National Centre of Competence in Research (NCCR) for materials by design (MARVEL).
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