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"Geiger, Simon"
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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
Electrifying model catalysts for understanding electrocatalytic reactions in liquid electrolytes
2018
Electrocatalysis is at the heart of our future transition to a renewable energy system. Most energy storage and conversion technologies for renewables rely on electrocatalytic processes and, with increasing availability of cheap electrical energy from renewables, chemical production will witness electrification in the near future1–3. However, our fundamental understanding of electrocatalysis lags behind the field of classical heterogeneous catalysis that has been the dominating chemical technology for a long time. Here, we describe a new strategy to advance fundamental studies on electrocatalytic materials. We propose to ‘electrify’ complex oxide-based model catalysts made by surface science methods to explore electrocatalytic reactions in liquid electrolytes. We demonstrate the feasibility of this concept by transferring an atomically defined platinum/cobalt oxide model catalyst into the electrochemical environment while preserving its atomic surface structure. Using this approach, we explore particle size effects and identify hitherto unknown metal–support interactions that stabilize oxidized platinum at the nanoparticle interface. The metal–support interactions open a new synergistic reaction pathway that involves both metallic and oxidized platinum. Our results illustrate the potential of the concept, which makes available a systematic approach to build atomically defined model electrodes for fundamental electrocatalytic studies.
Journal Article
Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution
by
Zeradjanin, Aleksandar
,
Mingers, Andrea
,
Geiger, Simon
in
639/166/898
,
639/638/161/892
,
639/638/224/685
2016
The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling
aqua regia
; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an ‘electrode-less’ process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable.
Given the scarcity and cost of platinum, it is important to develop sustainable processes for its recycling. Here, the authors report the dissolution of metallic platinum using reductive and oxidative gases to repetitively change its surface oxidation state, in the absence of an external electric current.
Journal Article
Structural insights into the recognition of cisplatin and AAF-dG lesion by Rad14 (XPA)
by
Karola L. Gasteiger
,
Sabine Schneider
,
Jochen Kuper
in
2-Acetylaminofluorene - chemistry
,
2-Acetylaminofluorene - metabolism
,
Amino Acid Sequence
2015
Nucleotide excision repair (NER) is responsible for the removal of a large variety of structurally diverse DNA lesions. Mutations of the involved proteins cause the xeroderma pigmentosum (XP) cancer predisposition syndrome. Although the general mechanism of the NER process is well studied, the function of the XPA protein, which is of central importance for successful NER, has remained enigmatic. It is known, that XPA binds kinked DNA structures and that it interacts also with DNA duplexes containing certain lesions, but the mechanism of interactions is unknown. Here we present two crystal structures of the DNA binding domain (DBD) of the yeast XPA homolog Rad14 bound to DNA with either a cisplatin lesion (1,2-GG) or an acetylaminofluorene adduct (AAF-dG). In the structures, we see that two Rad14 molecules bind to the duplex, which induces DNA melting of the duplex remote from the lesion. Each monomer interrogates the duplex with a β-hairpin, which creates a 13mer duplex recognition motif additionally characterized by a sharp 70° DNA kink at the position of the lesion. Although the 1,2-GG lesion stabilizes the kink due to the covalent fixation of the crosslinked dG bases at a 90° angle, the AAF-dG fully intercalates into the duplex to stabilize the kinked structure.
Journal Article
Influence of Support Material on the Structural Evolution of Copper during Electrochemical CO2 Reduction
2023
The copper‐catalyzed electrochemical CO2 reduction reaction represents an elegant pathway to reduce CO2 emissions while producing a wide range of valuable hydrocarbons. The selectivity for these products depends strongly on the structure and morphology of the copper catalyst. However, continued deactivation during catalysis alters the obtained product spectrum. In this work, we report on the stabilizing effect of three different carbon supports with unique pore structures. The influence of pore structure on stability and selectivity was examined by high‐angle annular dark field scanning transmission electron microscopy and gas chromatography measurements in a micro‐flow cell. Supporting particles into confined space was found to increase the barrier for particle agglomeration during 20 h of chronopotentiometry measurements at 100 mA cm−2 resembling long‐term CO2 reduction conditions. We propose a catalyst design preventing coalescence and agglomeration in harsh electrochemical reaction conditions, exemplarily demonstrated for the electrocatalytic CO2 reduction. With this work, we provide important insights into the design of stable CO2 electrocatalysts that can potentially be applied to a wide range of applications. Role of support: Post‐catalytic evaluation of three different carbon‐supported Cu CO2 reduction catalysts revealed a location‐dependent stabilization of nanoparticles in the support, with pore confinement showing anti‐agglomeration capabilities. Measured faradaic efficiency put previously reported particle size‐selectivity relations into question and highlight the need for post‐catalytic evaluation to elucidate structure‐selectivity relations.
Journal Article
N6-methyladenosine (m6A) recruits and repels proteins to regulate mRNA homeostasis
by
Rossa, Martin
,
Baltissen, Marijke P A
,
Jansen, Pascal W T C
in
631/45/475/2290
,
631/45/612/1230
,
Autism
2017
A comprehensive proteomics screen for ‘reader’ proteins that recognize m
6
A-modified RNA reveals that the modification both promotes and prevents the binding of factors that control mRNA homeostasis in mammalian cells.
RNA modifications are integral to the regulation of RNA metabolism. One abundant mRNA modification is
N
6
-methyladenosine (m
6
A), which affects various aspects of RNA metabolism, including splicing, translation and degradation. Current knowledge about the proteins recruited to m
6
A to carry out these molecular processes is still limited. Here we describe comprehensive and systematic mass-spectrometry-based screening of m
6
A interactors in various cell types and sequence contexts. Among the main findings, we identified G3BP1 as a protein that is repelled by m
6
A and positively regulates mRNA stability in an m
6
A-regulated manner. Furthermore, we identified FMR1 as a sequence-context-dependent m
6
A reader, thus revealing a connection between an mRNA modification and an autism spectrum disorder. Collectively, our data represent a rich resource and shed further light on the complex interplay among m
6
A, m
6
A interactors and mRNA homeostasis.
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
Influence of Support Material on the Structural Evolution of Copper during Electrochemical CO 2 Reduction
2023
The copper‐catalyzed electrochemical CO 2 reduction reaction represents an elegant pathway to reduce CO 2 emissions while producing a wide range of valuable hydrocarbons. The selectivity for these products depends strongly on the structure and morphology of the copper catalyst. However, continued deactivation during catalysis alters the obtained product spectrum. In this work, we report on the stabilizing effect of three different carbon supports with unique pore structures. The influence of pore structure on stability and selectivity was examined by high‐angle annular dark field scanning transmission electron microscopy and gas chromatography measurements in a micro‐flow cell. Supporting particles into confined space was found to increase the barrier for particle agglomeration during 20 h of chronopotentiometry measurements at 100 mA cm −2 resembling long‐term CO 2 reduction conditions. We propose a catalyst design preventing coalescence and agglomeration in harsh electrochemical reaction conditions, exemplarily demonstrated for the electrocatalytic CO 2 reduction. With this work, we provide important insights into the design of stable CO 2 electrocatalysts that can potentially be applied to a wide range of applications.
Journal Article
Using Instability of a Non-stoichiometric Mixed Oxide Oxygen Evolution Catalyst As a Tool to Improve Its Electrocatalytic Performance
by
Mingers, Andrea M
,
Mayrhofer, Karl J. J
,
Geiger, Simon
in
Acidic oxides
,
Catalysis
,
Catalysts
2018
Owing to their superior electrocatalytic performance, non-stoichiometric mixed oxides are often considered as promising electrocatalysts for the acidic oxygen evolution reaction (OER). Their activity and stability can be superior to those of the state-of-the-art IrO2 catalysts, although the exact nature of this phenomenon is not yet understood. In the current work, a Ir0.7Sn0.3O2-x thin-film electrode is taken as a representative example for a thorough evaluation of OER activity of the non-stoichiometric oxides. Complementary activity and stability analysis of Ir0.7Sn0.3O2-x electrodes is achieved using a setup based on an electrochemical scanning flow cell and ICP-MS. The obtained ICP-MS data presents an unambiguous proof of the preferential dissolution of the less noble Sn from the mixed oxide during OER. While less than a monolayer of Ir is dissolved after a prolonged electrolysis of 1400 min during which its dissolution rate drops to near zero, the amount of Sn lost is ten monolayers. The latter finding is confirmed by XPS analysis, which besides showing Ir surface enrichment also indicates a gradual transformation of Ir0 to IrIII species. This transition is beneficial for electrode activity, as the overpotential for OER at j = 5 mA cm−2 was decreasing up to 300 mV. The increase in electrode activity is attributed to several mechanisms including generation of IrIII active sites and overall surface area increase. A generalized description of OER catalysis by Ir-based materials is given, including data from the current work as well as from other Ir-based mixed oxides, such as Ir-Ru-O and Ir-Ni-O.[Images not available. See PDF.]Graphical Abstract
Journal Article