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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Bäumer, Christoph
University of Twente
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (30/30 displayed)
- 2024The effect of intrinsic magnetic order on electrochemical water splittingcitations
- 2024In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reactioncitations
- 2023Separating the Effects of Band Bending and Covalency in Hybrid Perovskite Oxide Electrocatalyst Bilayers for Water Electrolysis
- 2023Probing the stability of SrIrO3 during active water electrolysis via operando atomic force microscopycitations
- 2023Single-Source Vapor-Deposition of MA1–xFAxPbI3 Perovskite Absorbers for Solar Cellscitations
- 2023A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidationcitations
- 2022Atomistic Insights into Activation and Degradation of La0.6Sr0.4CoO3-δElectrocatalysts under Oxygen Evolution Conditionscitations
- 2022Separating the Effects of Band Bending and Covalency in Hybrid Perovskite Oxide Electrocatalyst Bilayers for Water Electrolysiscitations
- 2022A high entropy oxide as high-activity electrocatalyst for water oxidation
- 2022Activity-Stability Relationships in Oxide Electrocatalysts for Water Electrolysiscitations
- 2021In situ spectroscopic ellipsometry as a pathway toward achieving VO2 stoichiometry for amorphous vanadium oxide with magnetron sputteringcitations
- 2021Carbonate formation lowers the electrocatalytic activity of perovskite oxides for water electrolysiscitations
- 2020Antiphase Boundaries Constitute Fast Cation Diffusion Paths in SrTiO3 Memristive Devicescitations
- 2020Photoemission electron microscopy of magneto-ionic effects in La0.7Sr0.3MnO3citations
- 2020SrTiO3 termination controlcitations
- 2019Topotactic Phase Transition Driving Memristive Behaviorcitations
- 2019Electrolysis of Water at Atomically Tailored Epitaxial Cobaltite Surfacescitations
- 2018A Theoretical and Experimental View on the Temperature Dependence of the Electronic Conduction through a Schottky Barrier in a Resistively Switching SrTiO3-Based Memory Cellcitations
- 2018Addressing Multiple Resistive States of Polyoxovanadatescitations
- 2018A Theoretical and Experimental View on the Temperature Dependence of the Electronic Conduction through a Schottky Barrier in a Resistively Switching SrTiO 3 -Based Memory Cellcitations
- 2018Reduction of the forming voltage through tailored oxygen non-stoichiometry in tantalum oxide ReRAM devicescitations
- 2018Charge-transfer in B-site-depleted NdGaO3/SrTiO3 heterostructurescitations
- 2017Molecular Characteristics of a Mixed-Valence Polyoxovanadate {VIV/V18O42} in Solution and at the Liquid-Surface Interfacecitations
- 2015Surface Termination Conversion during SrTiO$_{3}$ Thin Film Growth Revealed by X-ray Photoelectron Spectroscopycitations
- 2015Complex behaviour of vacancy point-defects in SrRuO3 thin filmscitations
- 2015Ferroelectrically driven spatial carrier density modulation in graphenecitations
- 2015The influence of the local oxygen vacancy concentration on the piezoresponse of strontium titanate thin filmscitations
- 2015Surface Termination Conversion during SrTiO3 Thin Film Growth Revealed by X-ray Photoelectron Spectroscopycitations
- 2015Impact of the cation-stoichiometry on the resistive switching and data retention of SrTiO3 thin filmscitations
- 2013Feasibility studies for filament detection in resistively switching SrTiO3 devices by employing grazing incidence small angle X-ray scatteringcitations
Places of action
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article
Molecular Characteristics of a Mixed-Valence Polyoxovanadate {VIV/V18O42} in Solution and at the Liquid-Surface Interface
Abstract
<p>The understanding of the molecular state of vanadium-oxo clusters (polyoxovanadates, POVs) in solution and on surface is a key to their target application in catalysis as well as molecular electronics and spintronics. We here report the results of a combined experimental and computational study of the behavior of nucleophilic polyoxoanions [V<sup>IV</sup><sub>10</sub>V<sup>V</sup><sub>8</sub>O<sub>42</sub>(I)]<sup>5-</sup> charged balanced by Et<sub>4</sub>N<sup>+</sup> in water, in a one-phase organic solution of N,N-dimethylformamid (DMF) or acetonitrile (MeCN), in a mixed solution of MeCN-water, and at the hybrid liquid-surface interface. The molecular characteristics of the compound (NEt<sub>4</sub>)<sub>5</sub>[V<sub>18</sub>O<sub>42</sub>(I)] (1) in the given environments were studied by microspectroscopic, electrochemical, scattering, and molecular mechanics methods. Contrary to the situation in pure water, where we observe great agglomeration with a number of intercalated H<sub>2</sub>O molecules between POVs that are surrounded by the Et<sub>4</sub>N<sup>+</sup> ions, no or only minor agglomeration of redox-active POVs in an unprecedented cation-mediated fashion was detected in pure DMF and MeCN, respectively. An inclusion of 1% water in the MeCN solution does not have an effect significant enough to reinforce agglomeration; however, this leads to the POV⋯POV interface characterized by the presence of the Et<sub>4</sub>N<sup>+</sup> ions and a small number of H<sub>2</sub>O molecules. Water amounts of ≥5% trigger the formation of higher oligomers. The deposition of compound 1 from MeCN onto an Au(111) surface affords nearly round-shaped particles (∼10 nm). The use of DMF instead of MeCN results in bigger, irregularly shaped particles (∼30 nm). This change of solvent gives rise to more extensive intermolecular interactions between polyoxoanions and their countercations as well as weaker binding of ion-pairing induced agglomerates to the metallic substrate. Lower concentration of adsorbed molecules leads to a submonolayer coverage and an accompanied change of the POV's redox state, whereas their higher concentration results in a multilayer coverage that offers the pristine mixed-valence structure of the polyoxoanion. Our study provides first important insights into the reactivity peculiarities of this redox-responsive material class on a solid support.</p>