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36
result(s) for
"Mayrhofer, Karl J. J."
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Engineering stable electrocatalysts by synergistic stabilization between carbide cores and Pt shells
by
Paciok, Paul
,
Dunin-Borkowski, Rafal E.
,
Shao-Horn, Yang
in
639/301/299
,
639/638/161/893
,
639/638/77
2020
Core–shell particles with earth-abundant cores represent an effective design strategy for improving the performance of noble metal catalysts, while simultaneously reducing the content of expensive noble metals
1
–
4
. However, the structural and catalytic stabilities of these materials often suffer during the harsh conditions encountered in important reactions, such as the oxygen reduction reaction (ORR)
3
–
5
. Here, we demonstrate that atomically thin Pt shells stabilize titanium tungsten carbide cores, even at highly oxidizing potentials. In situ, time-resolved experiments showed how the Pt coating protects the normally labile core against oxidation and dissolution, and detailed microscopy studies revealed the dynamics of partially and fully coated core–shell nanoparticles during potential cycling. Particles with complete Pt coverage precisely maintained their core–shell structure and atomic composition during accelerated electrochemical ageing studies consisting of over 10,000 potential cycles. The exceptional durability of fully coated materials highlights the potential of core–shell architectures using earth-abundant transition metal carbide (TMC) and nitride (TMN) cores for future catalytic applications.
Using core–shell particles represents an effective design strategy for improving the performance of noble metal catalysts, but their stabilities can suffer during reactions. Atomically thin Pt shells are shown to stabilize titanium tungsten carbide cores, even at highly oxidizing potentials.
Journal Article
Scalable synthesis of NiFe-layered double hydroxide for efficient anion exchange membrane electrolysis
2025
The alkaline oxygen evolution reaction is a key step in producing green hydrogen through water electrolysis, but its large-scale industrial application remains limited due to challenges with current electrocatalysts—particularly in terms of scalability, efficiency, and long-term stability. Here we show an industrially scalable synthesis of an active NiFe layered double hydroxide (NiFe-LDH) catalyst using a room-temperature, atmospheric-pressure route. The process involves homogeneous alkalinization, where chloride ions nucleophilically attack an epoxide ring, producing a low-dimensional, defect-rich NiFe-LDH with pronounced iron clustering. In-situ spectroscopy and ab-initio calculations reveal that these structural features maximize the conversion of the NiFe-LDH to the catalytic active phase and minimize the energy barrier, improving catalytic efficiency. When used as the anode in an anion exchange membrane water electrolyzer operating at 70 °C, our material delivers 1 A cm⁻² at 1.69 V in a 5 cm
2
full-cell setup, with notable durability compared to conventional NiFe-LDHs. This scalable approach could considerably lower the cost of green hydrogen production by enabling more efficient alkaline electrolyzers.
Green hydrogen production via water electrolysis requires a low-cost solution to provide efficient catalysts. Here, the authors report an industrially scalable method for synthesizing NiFe layered double hydroxide at room temperature and atmospheric pressure, enhancing alkaline electrolysis.
Journal Article
The effect of particle proximity on the oxygen reduction rate of size-selected platinum clusters
by
Roefzaad, Melanie
,
Ulrich Biedermann, P.
,
Heiz, Ueli
in
639/301/299/886
,
639/301/357/354
,
639/638/298
2013
The diminished surface-area-normalized catalytic activity of highly dispersed Pt nanoparticles compared with bulk Pt is particularly intricate, and not yet understood. Here we report on the oxygen reduction reaction (ORR) activity of well-defined, size-selected Pt nanoclusters; a unique approach that allows precise control of both the cluster size and coverage, independently. Our investigations reveal that size-selected Pt nanoclusters can reach extraordinarily high ORR activities, especially in terms of mass-normalized activity, if deposited at high coverage on a glassy carbon substrate. It is observed that the Pt cluster coverage, and hence the interparticle distance, decisively influence the observed catalytic activity and that closely packed assemblies of Pt clusters approach the surface activity of bulk Pt. Our results open up new strategies for the design of catalyst materials that circumvent the detrimental dispersion effect, and may eventually allow the full electrocatalytic potential of Pt nanoclusters to be realized.
The catalytic activity of highly dispersed platinum nanoparticles is not yet well understood. Now, a unique approach that allows precise control of both the size and coverage of platinum nanoclusters reveals that particle proximity influences the oxygen reduction rate of these size-selected clusters, especially in terms of mass normalized activity.
Journal Article
Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst
2016
Maximum atom efficiency as well as distinct chemoselectivity is expected for electrocatalysis on atomically dispersed (or single site) metal centres, but its realization remains challenging so far, because carbon, as the most widely used electrocatalyst support, cannot effectively stabilize them. Here we report that a sulfur-doped zeolite-templated carbon, simultaneously exhibiting large sulfur content (17 wt% S), as well as a unique carbon structure (that is, highly curved three-dimensional networks of graphene nanoribbons), can stabilize a relatively high loading of platinum (5 wt%) in the form of highly dispersed species including site isolated atoms. In the oxygen reduction reaction, this catalyst does not follow a conventional four-electron pathway producing H
2
O, but selectively produces H
2
O
2
even over extended times without significant degradation of the activity. Thus, this approach constitutes a potentially promising route for producing important fine chemical H
2
O
2
, and also offers opportunities for tuning the selectivity of other electrochemical reactions on various metal catalysts.
Atomically dispersed metal catalysts display high atom efficiency for electrocatalytic processes. Here, the authors report that sulfur-doped zeolite-templated carbon stabilizes highly dispersed platinum species, predominantly as single-atom centres, and probe its oxygen reduction selectivity.
Journal Article
Analysing the relationship between the fields of thermo- and electrocatalysis taking hydrogen peroxide as a case study
by
Lewis, Richard J.
,
Freakley, Simon J.
,
Ledendecker, Marc
in
639/638/224/685
,
639/638/77/886
,
639/638/77/887
2022
Catalysis is inherently driven by the interaction of reactants, intermediates and formed products with the catalyst’s surface. In order to reach the desired transition state and to overcome the kinetic barrier, elevated temperatures or electrical potentials are employed to increase the rate of reaction. Despite immense efforts in the last decades, research in thermo- and electrocatalysis has often preceded in isolation, even for similar reactions. Conceptually, any heterogeneous surface process that involves changes in oxidation states, redox processes, adsorption of charged species (even as spectators) or heterolytic cleavage of small molecules should be thought of as having parallels with electrochemical processes occurring at electrified interfaces. Herein, we compare current trends in thermo- and electrocatalysis and elaborate on the commonalities and differences between both research fields, with a specific focus on the production of hydrogen peroxide as case study. We hope that interlinking both fields will be inspiring and thought-provoking, eventually creating synergies and leverage towards more efficient decentralized chemical conversion processes.
Research in thermo- and electrocatalysis have often preceded in isolation, even for similar reactions. Here, the authors compare current trends in both fields and elaborate on the commonalities and differences with a specific focus on the production of hydrogen peroxide.
Journal Article
Towards maximized utilization of iridium for the acidic oxygen evolution reaction
by
Ledendecker, Marc
,
Geiger, Simon
,
Mayrhofer, Karl J. J.
in
Atomic layer epitaxy
,
Atomic/Molecular Structure and Spectra
,
Biomedicine
2019
The reduction in noble metal content for efficient oxygen evolution catalysis is a crucial aspect towards the large scale commercialisation of polymer electrolyte membrane electrolyzers. Since catalytic stability and activity are inversely related, long service lifetime still demands large amounts of low-abundant and expensive iridium. In this manuscript we elaborate on the concept of maximizing the utilisation of iridium for the oxygen evolution reaction. By combining different tin oxide based support materials with liquid atomic layer deposition of iridium oxide, new possibilities are opened up to grow thin layers of iridium oxide with tuneable noble metal amounts.
In-situ
, time- and potential-resolved dissolution experiments reveal how the stability of the substrate and the catalyst layer thickness directly affect the activity and stability of deposited iridium oxide. Based on our results, we elaborate on strategies how to obtain stable and active catalysts with maximized iridium utilisation for the oxygen evolution reaction and demonstrate how the activity and durability can be tailored correspondingly. Our results highlight the potential of utilizing thin noble metal films with earth abundant support materials for future catalytic applications in the energy sector.
Journal Article
Stability limits of tin-based electrocatalyst supports
2017
Tin-based oxides are attractive catalyst support materials considered for application in fuel cells and electrolysers. If properly doped, these oxides are relatively good conductors, assuring that ohmic drop in real applications is minimal. Corrosion of dopants, however, will lead to severe performance deterioration. The present work aims to investigate the potential dependent dissolution rates of indium tin oxide (ITO), fluorine doped tin oxide (FTO) and antimony doped tin oxide (ATO) in the broad potential window ranging from −0.6 to 3.2 V
RHE
in 0.1 M H
2
SO
4
electrolyte. It is shown that in the cathodic part of the studied potential window all oxides dissolve during the electrochemical reduction of the oxide –
cathodic dissolution
. In case an oxidation potential is applied to the reduced electrode, metal oxidation is accompanied with additional dissolution –
anodic dissolution
. Additional dissolution is observed during the oxygen evolution reaction. FTO withstands anodic conditions best, while little and strong dissolution is observed for ATO and ITO, respectively. In discussion of possible corrosion mechanisms, obtained dissolution onset potentials are correlated with existing thermodynamic data.
Journal Article
The stability number as a metric for electrocatalyst stability benchmarking
by
Oellers, Tobias
,
Fu, Wen Tian
,
Geiger, Simon
in
639/301/299/161
,
639/4077/4079/4088
,
639/638/161/886
2018
Reducing the noble metal loading and increasing the specific activity of the oxygen evolution catalysts are omnipresent challenges in proton-exchange-membrane water electrolysis, which have recently been tackled by utilizing mixed oxides of noble and non-noble elements. However, proper verification of the stability of these materials is still pending. Here we introduce a metric to explore the dissolution processes of various iridium-based oxides, defined as the ratio between the amounts of evolved oxygen and dissolved iridium. The so-called stability number is independent of loading, surface area or involved active sites and provides a reasonable comparison of diverse materials with respect to stability. The case study on iridium-based perovskites shows that leaching of the non-noble elements in mixed oxides leads to the formation of highly active amorphous iridium oxide, the instability of which is explained by the generation of short-lived vacancies that favour dissolution. These insights are meant to guide further research, which should be devoted to increasing the utilization of highly durable pure crystalline iridium oxide and finding solutions to stabilize amorphous iridium oxides.
The proper verification of the stability of metal oxide catalysts for water electrolysis in acid electrolyte remains unresolved. Here, the ‘stability number’ is introduced to evaluate the dissolution mechanisms of various iridium-based oxides and to facilitate benchmarking of catalysts independent of loading, surface area or involved active sites.
Journal Article
Photodeposition‐Based Synthesis of TiO2@IrOx Core–Shell Catalyst for Proton Exchange Membrane Water Electrolysis with Low Iridium Loading
2024
The widespread application of green hydrogen production technologies requires cost reduction of crucial elements. To achieve this, a viable pathway to reduce the iridium loading in proton exchange membrane water electrolysis (PEMWE) is explored. Herein, a scalable synthesis method based on a photodeposition process for a TiO2@IrOx core–shell catalyst with a reduced iridium content as low as 40 wt.% is presented. Using this synthesis method, titania support particles homogeneously coated with a thin iridium oxide shell of only 2.1 ± 0.4 nm are obtained. The catalyst exhibits not only high ex situ activity, but also decent stability compared to commercially available catalysts. Furthermore, the unique core–shell structure provides a threefold increased electrical powder conductivity compared to structures without the shell. In addition, the low iridium content facilitates the fabrication of sufficiently thick catalyst layers at decreased iridium loadings mitigating the impact of crack formation in the catalyst layer during PEMWE operation. It is demonstrated that the novel TiO2@IrOx core–shell catalyst clearly outperforms the commercial reference in single‐cell tests with an iridium loading below 0.3 mgIr cm−2 exhibiting a superior iridium‐specific power density of 17.9 kW gIr−1 compared to 10.4 kW gIr−1 for the commercial reference. A facile and scalable synthesis method for a TiO2@IrOx core–shell electrocatalyst is developed, and its stability and superior performance for the acidic oxygen evolution reaction compared to a commercial catalyst is demonstrated in both ex situ and single‐cell electrochemical measurements.
Journal Article
Formation of lithiated gold and its use for the preparation of reference electrodes — an EQCM study
by
Berkes, Balázs B
,
Behling, Christopher
,
Mayrhofer, Karl J. J
in
Alloys
,
Batteries
,
Electrochemical cells
2021
Lithiated gold wires can be used to build reference electrodes with outstanding potential stabilities over several days and even over the course of one year. These electrodes are well suited for investigations in the context of lithium-ion batteries (LIBs). In this work, a detailed procedure for the preparation of such electrodes with tailored mechanical properties, which can be fitted gastight into electrochemical cells using commercially available fittings, is given. The electrochemical lithiation process is studied using the electrochemical quartz crystal microbalance (EQCM) technique, and the differences in lithiation of wire type and thin film type gold electrodes are discussed. All experiments were carried out with two different electrolytes, namely, a LiPF6 and a lithium bis(trifluoromethane sulfonyl) imide (LiTFSI)-based electrolyte, and we conclude that for a higher lithiation rate and long-term stability, the use of LiTFSI-based electrolyte in the preparation phase is beneficial. The EQCM data provides a better insight in the analysis of film formation processes, like the buildup of the solid electrolyte interphase (SEI) during the lithiation, the rate of deposition of metallic lithium, or additional information on the kinetics of Li-Au alloy formation.
Journal Article