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14
result(s) for
"Göhl, Daniel"
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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
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
Engineering gold-platinum core-shell nanoparticles by self-limitation in solution
by
Paciok, Paul
,
Osowiecki, Wojciech T.
,
Pander, Marc
in
639/301/299/886
,
639/301/357/551
,
639/4077
2022
Core-shell particles with thin noble metal shells represent an attractive material class with potential for various applications ranging from catalysis to biomedical and pharmaceutical applications to optical crystals. The synthesis of well-defined core-shell architectures remains, however, highly challenging. Here, we demonstrate that atomically-thin and homogeneous platinum shells can be grown via a colloidal synthesis method on a variety of gold nanostructures ranging from spherical nanoparticles to nanorods and nanocubes. The synthesis is based on the exchange of low binding citrate ligands on gold, the reduction of platinum and the subsequent kinetically hindered growth by carbon monoxide as strong binding ligand. The prerequisites for homogeneous growth are low core-binding ligands with moderate fast ligand exchange in solution, a mild reducing agent to mitigate homonucleation and a strong affinity of a second ligand system that can bind to the shell’s surface. The simplicity of the described synthetic route can potentially be adapted to various other material libraries to obtain atomically smooth core-shell systems.
Core-shell particles with thin noble metal shells represent an attractive material class with potential for various applications ranging from catalysis to biomedical applications, but the synthesis of well-defined core-shell architectures remains highly challenging. Here, the authors report the chemically induced self-limiting growth of atomically-thin and homogeneous platinum shells on a variety of gold nanostructures.
Journal Article
Core‐passivation: A concept for stable core‐shell nanoparticles in aqueous electrocatalysis
by
Paciok, Paul
,
Ledendecker, Marc
,
Mayrhofer, Karl J. J.
in
Aqueous solutions
,
Core-shell particles
,
Electrocatalysis
2023
The stability of nanoparticles is a major challenge in thermal and electrocatalysis. This is especially true for core‐shell nanoparticles where only a few monolayers of noble metal protect the usually non‐noble core material. In this work, we utilize the practical nobility concept to engineer stable core‐shell nanoparticles with a self‐passivating core material. Specifically, tantalum carbide as core material in combination with a 1–3 monolayer thick platinum shell exhibits exceptional stability in aqueous media. The core‐shell catalyst shows no sign of structural changes after 10,000 degradation cycles up to 1.0 VRHE. Due to the efficient passivation of tantalum carbide at the solid/liquid interface, the dissolution reduces by a factor of eight compared to bare Pt. Our findings confirm that passivating core materials are highly beneficial for the stabilization of core‐shell nanomaterials in aqueous media. They open up new ways for the rational design of cost‐efficient but stable non‐noble core – platinum shell nanoparticles where harsh, oxidizing conditions are employed. Core‐shell particle with a self‐passivating core allows for the design of active and stable electrocatalysts for the oxygen reduction reaction. Core‐shell nanoparticles with non‐noble core elements are susceptible to degradation and dissolution. Here, we report on tantalum carbide nanoparticles that are covered with an atomically thin platinum shell. The synthesized nanoparticles are highly active for the electrochemical oxygen reduction reaction by forming a self‐healing oxide film at the solid/liquid interface and are stable over 10,000 degradation cycles.
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
Nociceptive interneurons control modular motor pathways to promote escape behavior in Drosophila
2018
Rapid and efficient escape behaviors in response to noxious sensory stimuli are essential for protection and survival. Yet, how noxious stimuli are transformed to coordinated escape behaviors remains poorly understood. In Drosophila larvae, noxious stimuli trigger sequential body bending and corkscrew-like rolling behavior. We identified a population of interneurons in the nerve cord of Drosophila, termed Down-and-Back (DnB) neurons, that are activated by noxious heat, promote nociceptive behavior, and are required for robust escape responses to noxious stimuli. Electron microscopic circuit reconstruction shows that DnBs are targets of nociceptive and mechanosensory neurons, are directly presynaptic to pre-motor circuits, and link indirectly to Goro rolling command-like neurons. DnB activation promotes activity in Goro neurons, and coincident inactivation of Goro neurons prevents the rolling sequence but leaves intact body bending motor responses. Thus, activity from nociceptors to DnB interneurons coordinates modular elements of nociceptive escape behavior.
Journal Article
A rapid, cost-effective tailed amplicon method for sequencing SARS-CoV-2
by
Watson, Ray H. B.
,
Grady, Patrick
,
Beckman, Kenneth B.
in
Animal Genetics and Genomics
,
Benchmarking
,
Binding sites
2020
Background
The global COVID-19 pandemic has led to an urgent need for scalable methods for clinical diagnostics and viral tracking. Next generation sequencing technologies have enabled large-scale genomic surveillance of SARS-CoV-2 as thousands of isolates are being sequenced around the world and deposited in public data repositories. A number of methods using both short- and long-read technologies are currently being applied for SARS-CoV-2 sequencing, including amplicon approaches, metagenomic methods, and sequence capture or enrichment methods. Given the small genome size, the ability to sequence SARS-CoV-2 at scale is limited by the cost and labor associated with making sequencing libraries.
Results
Here we describe a low-cost, streamlined, all amplicon-based method for sequencing SARS-CoV-2, which bypasses costly and time-consuming library preparation steps. We benchmark this tailed amplicon method against both the ARTIC amplicon protocol and sequence capture approaches and show that an optimized tailed amplicon approach achieves comparable amplicon balance, coverage metrics, and variant calls to the ARTIC v3 approach.
Conclusions
The tailed amplicon method we describe represents a cost-effective and highly scalable method for SARS-CoV-2 sequencing.
Journal Article
NCOA5 deficiency promotes a unique liver protumorigenic microenvironment through p21WAF1/CIP1 overexpression, which is reversed by metformin
2020
Prevention and treatment options for hepatocellular carcinoma (HCC) are presently limited, underscoring the necessity for further elucidating molecular mechanisms underlying HCC development and identifying new prevention and therapeutic targets. Here, we demonstrate a unique protumorigenic niche in the livers of Ncoa5+/− mouse model of HCC, which is characterized by altered expression of a subset of genes including p21WAF1/CIP1 and proinflammatory cytokine genes, increased putative hepatic progenitors, and expansions of activated and tissue-resident memory (TRM) CD8+ T lymphocytes, myeloid-derived suppressor cells (MDSCs), and alternatively activated M2 macrophages. Importantly, prophylactic metformin treatment reversed these characteristics including aberrant p21WAF1/CIP1 expression and subsequently reduced HCC incidence in Ncoa5+/− male mice. Heterozygous deletion of the p21WAF1/CIP1 gene alleviated the key features associated with the protumorigenic niche in the livers of Ncoa5+/− male mice. Moreover, transcriptomic analysis reveals that preneoplastic livers of Ncoa5+/− mice are similar to the livers of nonalcoholic steatohepatitis patients as well as the adjacent noncancerous liver tissues of a subset of HCC patients with a relatively poor prognosis. Together, our results suggest that p21WAF1/CIP1 overexpression is essential in the development of protumorigenic microenvironment induced by NCOA5 deficiency and metformin prevents HCC development via alleviating p21WAF1/CIP1 overexpression and protumorigenic microenvironment.
Journal Article
Rhinovirus prevalence as indicator for efficacy of measures against SARS-CoV-2
2021
Background
Non-pharmaceutical measures to control the spread of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) should be carefully tuned as they can impose a heavy social and economic burden. To quantify and possibly tune the efficacy of these anti-SARS-CoV-2 measures, we have devised indicators based on the abundant historic and current prevalence data from other respiratory viruses.
Methods
We obtained incidence data of 17 respiratory viruses from hospitalized patients and outpatients collected by 37 clinics and laboratories between 2010-2020 in Germany. With a probabilistic model for Bayes inference we quantified prevalence changes of the different viruses between months in the pre-pandemic period 2010-2019 and the corresponding months in 2020, the year of the pandemic with noninvasive measures of various degrees of stringency.
Results
We discovered remarkable reductions
δ
in rhinovirus (RV) prevalence by about 25% (95% highest density interval (HDI) [−0.35,−0.15]) in the months after the measures against SARS-CoV-2 were introduced in Germany. In the months after the measures began to ease, RV prevalence increased to low pre-pandemic levels, e.g. in August 2020
δ
=−0.14 (95% HDI [−0.28,0.12]).
Conclusions
RV prevalence is negatively correlated with the stringency of anti-SARS-CoV-2 measures with only a short time delay. This result suggests that RV prevalence could possibly be an indicator for the efficiency for these measures. As RV is ubiquitous at higher prevalence than SARS-CoV-2 or other emerging respiratory viruses, it could reflect the efficacy of noninvasive measures better than such emerging viruses themselves with their unevenly spreading clusters.
Journal Article
Angular distribution measurement of gamma rays from inelastic neutron scattering on 56Fe at the nELBE time-of-flight facility
by
Szücs, Tamás
,
Bemmerer, Daniel
,
Massarczyk, Ralph
in
Angular distribution
,
Angular position
,
Computer simulation
2017
Inelastic neutron scattering from 56Fe was studied at the nELBE time-of-flight facility. The incoming neutron energy ranges from 100 keV to 10 MeV in the fast neutron spectrum, where high precision nuclear data are needed. A detector setup has been installed to investigate the γ-ray angular distributions. It contains five HPGe and five LaBr3 detectors positioned at 30, 55, 90, 125 and 150 degrees relative to the beam axis. The intrinsic and the neutron induced background from the setup was subtracted by cyclical measurements with and without the natural Fe-target. Corrections for extended source efficiency and gamma-self-absorption, inside the target, were done using GEANT4 simulations. The angular distributions measured with the HPGe detectors are compared with earlier data. High neutron energy resolution up to a few keV was obtained with the LaBr3 detectors due to their much better time resolution.
Conference Proceeding