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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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Fermín, David J.
University of Bristol
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (37/37 displayed)
- 2024Activating Mn Sites by Ni Replacement in α-MnO2citations
- 2024Correlating molecular precursor interactions with device performance in solution-processed Cu2ZnSn(S,Se)4 thin-film solar cellscitations
- 2022Correlating Orbital Composition and Activity of LaMnxNi1–xO3 Nanostructures toward Oxygen Electrocatalysiscitations
- 2021Electrocatalytic Site Activity Enhancement via Orbital Overlap in A 2MnRuO 7(A = Dy 3+, Ho 3+, and Er 3+) Pyrochlore Nanostructurescitations
- 2020High Interfacial Hole‐Transfer Efficiency at GaFeO3 Thin Film Photoanodescitations
- 2020Pulsed laser deposition of single phase n- and p-type Cu2O thin films with low resistivitycitations
- 2020Promoting Active Electronic States in LaFeO3 Thin-Films Photocathodes via Alkaline-Earth Metal Substitutioncitations
- 2019Doping and alloying of kesteritescitations
- 2019Photovoltaic Performance of Phase-Pure Orthorhombic BiSI Thin-Filmscitations
- 2018Insights into the durability of Co-Fe spinel oxygen evolution electrocatalystscitations
- 2018Impact of Sb and Na Doping on the Surface Electronic Landscape of Cu2ZnSnS4 Thin Filmscitations
- 2018Investigating the Role of the Organic Cation in Formamidinium Lead Iodide Perovskite Using Ultrafast Spectroscopycitations
- 2018AMnO3 (A = Sr, La, Ca, Y) Perovskite Oxides as Oxygen Reduction Electrocatalystscitations
- 2017YFeO3 Photocathodes for Hydrogen Evolutioncitations
- 2017Textured PbI2 photocathodes obtained by gas phase anion replacementcitations
- 2017Single molecular precursor solution for CuIn(S,Se)2 thin films photovoltaic cellscitations
- 2017Solution Processed Single-Phase Cu2SnS3 filmscitations
- 2017Spectroscopic and electrical signatures of acceptor states in solution processed Cu2ZnSn(S,Se)4 solar cellscitations
- 2017Real-Time Tracking of Metal Nucleation via Local Perturbation of Hydration Layerscitations
- 2017YFeO 3 Photocathodes for Hydrogen Evolutioncitations
- 2016Cu2ZnSnS4 thin-films generated from a single solution based precursorcitations
- 2016Influence of thermal treatments on the stability of Pd nanoparticles supported on graphitised ordered mesoporous carbonscitations
- 2016A Synthetic Route for the Effective Preparation of Metal Alloy Nanoparticles and Their Use as Active Electrocatalystscitations
- 2015Crystal structure and defects visualization of Cu2ZnSnS4 nanoparticles employing transmission electron microscopy and electron diffractioncitations
- 2015Surface Activation of Pt Nanoparticles Synthesised by "Hot Injection" in the Presence of Oleylaminecitations
- 2015Growth of Epitaxial Pt<inf>1-x</inf>Pb<inf>x</inf> Alloys by Surface Limited Redox Replacement and Study of Their Adsorption Propertiescitations
- 2015Crystal structure and defects visualization of Cu 2 ZnSnS 4 nanoparticles employing transmission electron microscopy and electron diffractioncitations
- 2015Solution processed bismuth ferrite thin films for all-oxide solar photovoltaicscitations
- 2015Fast One-Pot Synthesis of MoS2/Crumpled Graphene p-n Nanonjunctions for Enhanced Photoelectrochemical Hydrogen Productioncitations
- 2015High surface area diamond-like carbon electrodes grown on vertically aligned carbon nanotubescitations
- 2013Electrochemical crystallization of spatially organized copper microwire arrays within biomineralized (dentine) templatescitations
- 2013Structure and Band Edge Energy of Highly Luminescent CdSei(1-x)Te(x) Alloyed Quantum Dotscitations
- 2012Electrocatalytic Properties of Strained Pd Nanoshells at Au Nanostructures: CO and HCOOH Oxidationcitations
- 2011Hydrogen Adsorption at Strained Pd Nanoshellscitations
- 2005Adsorption and photoreactivity of CdSe nanoparticles at liquid|liquid interfacescitations
- 2004Electrochemical and optical properties of two dimensional electrostatic assembly of Au nanocrystalscitations
- 2003Photoinduced electron transfer at liquid vertical bar liquid interfaces. Part VII. Correlation between self-organisation and structure of water-soluble photoactive speciescitations
Places of action
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article
Electrocatalytic Site Activity Enhancement via Orbital Overlap in A 2MnRuO 7(A = Dy 3+, Ho 3+, and Er 3+) Pyrochlore Nanostructures
Abstract
Oxygen electrocatalysis at transition metal oxides is one of the key challenges underpinning electrochemical energy conversion systems, involving a delicate interplay of bulk electronic structure and surface coordination of the active sites. In this work, we investigate for the first time the structure-activity relationship of A2RuMnO7 (A = Dy3+, Ho3+, Er3+) nanoparticles, demonstrating how orbital mixing of Ru, Mn, and O promotes high density of states (DOS) at the appropriate energy range for oxygen electrocatalysis. The bulk and surface structure of these multicomponent pyrochlores are investigated by high-resolution transmission electron microscopy, X-ray diffraction, X-ray absorption (XAS), X-ray emission (XES) and X-ray photoemission (XPS) spectroscopies. The materials exhibit high phase purity (cubic fcc with a space group Fd3 ̅m), in which variations in M-O bonds length are less than 1% upon replacing the A-site lanthanide. XES and XPS show that the mean oxidation state at the Mn-site as well as the nanoparticle surface composition were slightly affected by the lanthanide. The pyrochlore nanoparticles are significantly more active than the binary RuO2 and MnO2 towards the 4-electron oxygen reduction reaction (ORR) in alkaline solutions. Interestingly, normalization of kinetic parameters by the number density of electroactive sites concludes that Dy2RuMnO7 shows twice higher activity than benchmark materials such as LaMnO3. Analysis of the electrochemical profiles supported by DFT calculations reveals that the origin of the enhanced catalytic activity is linked to the mixing of Ru and Mn d-orbitals and O p-orbitals at the conduction band which strongly overlap with the formal redox energy of O2 in solution. The activity enhancement strongly manifests in the case of Dy2RuMnO7 where Ru/Mn ratio is closer to 1 in comparison with the Ho3+ and Er3+ analogs. These electronic effects are discussed in the context of the Gerischer formalism for electron transfer at the semiconductor/electrolyte junctions.