ORCID Profile
0000-0003-3989-0365
Current Organisation
Friedrich-Alexander-Universität Erlangen-Nürnberg
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Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0CP00345J
Abstract: The adsorption and reaction of ethylene on Pt/CeO(2-x)/Cu(111) model catalysts were studied by means of high resolution photoelectron spectroscopy (HR-PES) in conjunction with resonant photoemission spectroscopy (RPES). The dehydrogenation mechanism is compared to the HR-PES data obtained on a Pt(111) single crystal under identical conditions. It was found that the Pt nanoparticle system shows a substantially enhanced reactivity and several additional reaction pathways. In sharp contrast to Pt(111), partial dehydrogenation of ethylene on the supported Pt nanoparticles already starts at temperatures as low as 100 K. Similar to the single crystal surface, dehydrogenation occurs via the isomer ethylidene (CHCH(3)) and then mainly via ethylidyne (CCH(3)). In the temperature region between 100 and 250 K there is strong evidence for spillover of hydrocarbon fragments to the ceria support. In addition, splitting of ethylene to C(1) fragments is more facile than on Pt(111), giving rise to the formation of CH species and CO in the temperature region between 250 and 400 K. Upon further annealing, carbonaceous deposits are formed at 450 K. By heating to 700 K, these carbon deposits are completely removed from the surface by reaction with oxygen, provided by reverse spillover of oxygen from the ceria support.
Publisher: American Chemical Society (ACS)
Date: 05-06-2013
DOI: 10.1021/JP311008V
Publisher: American Chemical Society (ACS)
Date: 04-06-2015
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6CP00627B
Abstract: Formation of at least two oxygen vacancies triggers the reduction of one Pt 2+ species.
Publisher: American Chemical Society (ACS)
Date: 20-08-2018
Publisher: IOP Publishing
Date: 04-02-2021
Abstract: 2-Propanol and its dehydrogenated counterpart acetone can be used as a rechargeable electrofuel. The concept involves selective oxidation of 2-propanol to acetone in a fuel cell coupled with reverse catalytic hydrogenation of acetone to 2-propanol in a closed cycle. We studied electrocatalytic oxidation of 2-propanol on complex model Pt/Co 3 O 4 (111) electrocatalysts prepared in ultra-high vacuum and characterized by scanning tunneling microscopy. The electrocatalytic behavior of the model electrocatalysts has been investigated in alkaline media (pH 10, phosphate buffer) by means of electrochemical infrared reflection absorption spectroscopy and ex-situ emersion synchrotron radiation photoelectron spectroscopy as a function of Pt particle size and compared with the electrocatalytic behavior of Pt(111) and pristine Co 3 O 4 (111) electrodes under similar conditions. We found that the Co 3 O 4 (111) film is inactive towards electrochemical oxidation of 2-propanol under the electrochemical conditions (0.3–1.1 V RHE ). The electrochemical oxidation of 2-propanol readily occurs on Pt(111) yielding acetone at an onset potential of 0.4 V RHE . The reaction pathway does not involve CO but yields strongly adsorbed acetone species leading to a partial poisoning of the surface sites. On model Pt/Co 3 O 4 (111) electrocatalysts, we observed distinct metal support interactions and particle size effects associated with the charge transfer at the metal/oxide interface. We found that ultra-small Pt particles (around 1 nm and below) consist of partially oxidized Pt δ + species which show minor activity towards 2-propanol oxidation. In contrast, conventional Pt particles (particle size of a few nm) are mainly metallic and show high activity toward 2-propanol oxidation.
Publisher: Elsevier BV
Date: 2012
Publisher: Elsevier BV
Date: 30-09-2010
Publisher: Springer Science and Business Media LLC
Date: 20-03-2011
DOI: 10.1038/NMAT2976
Abstract: Interactions of metal particles with oxide supports can radically enhance the performance of supported catalysts. At the microscopic level, the details of such metal-oxide interactions usually remain obscure. This study identifies two types of oxidative metal-oxide interaction on well-defined models of technologically important Pt-ceria catalysts: (1) electron transfer from the Pt nanoparticle to the support, and (2) oxygen transfer from ceria to Pt. The electron transfer is favourable on ceria supports, irrespective of their morphology. Remarkably, the oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt and, thus, is inherently a nanoscale effect. Our findings enable us to detail the formation mechanism of the catalytically indispensable Pt-O species on ceria and to elucidate the extraordinary structure-activity dependence of ceria-based catalysts in general.
Publisher: Elsevier BV
Date: 06-2021
Publisher: Wiley
Date: 02-10-2013
Abstract: From a different angle: Thin films of functionalized ionic liquids are deposited on cerium oxides following a surface science approach. The functionalization of the alkyl chain changes its orientation with respect to the surface plane from normal to parallel. This then leads to a different surface chemistry at higher temperatures.
Publisher: American Chemical Society (ACS)
Date: 29-04-2016
Publisher: American Chemical Society (ACS)
Date: 14-05-2012
DOI: 10.1021/JP212237X
Publisher: American Chemical Society (ACS)
Date: 13-12-2012
DOI: 10.1021/JZ301856A
Abstract: Practical applications of ionic liquids (ILs) often involve IL/oxide interfaces, but little is known regarding their interfacial chemistry. The unusual physicochemical properties of ILs, including their exceptionally low vapor pressure, provide access to such interfaces using a surface science approach in ultrahigh vacuum (UHV). We have applied synchrotron radiation photoelectron spectroscopy (SR-PES) to the study of a thin film of the ionic liquid [C6C1Im][Tf2N] prepared in situ in UHV on ordered stoichiometric CeO2(111) and partially reduced CeO2-x. On the partially reduced surface, we mostly observe decomposition of the anion. On the stoichiometric CeO2(111) surface, however, a layer of surface-anchored organic products with high thermal stability is formed upon reaction of the cation. The suggested acid-base reaction pathway may provide well-defined functionalized IL/solid interfaces on basic oxides.
Publisher: Wiley
Date: 11-06-2014
Abstract: Platinum is the most versatile element in catalysis, but it is rare and its high price limits large-scale applications, for ex le in fuel-cell technology. Still, conventional catalysts use only a small fraction of the Pt content, that is, those atoms located at the catalyst's surface. To maximize the noble-metal efficiency, the precious metal should be atomically dispersed and exclusively located within the outermost surface layer of the material. Such atomically dispersed Pt surface species can indeed be prepared with exceptionally high stability. Using DFT calculations we identify a specific structural element, a ceria "nanopocket", which binds Pt(2+) so strongly that it withstands sintering and bulk diffusion. On model catalysts we experimentally confirm the theoretically predicted stability, and on real Pt-CeO2 nanocomposites showing high Pt efficiency in fuel-cell catalysis we also identify these anchoring sites.
Publisher: American Chemical Society (ACS)
Date: 11-03-2019
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4CP01632G
Abstract: We have studied the interaction of H2 with Pt-Sn nanoalloys supported on Sn-Ce mixed oxide films of different composition by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The model catalysts are prepared in a three step procedure that involves (i) the preparation of well-ordered CeO2(111) films on Cu(111) followed by subsequent physical vapor deposition of (ii) metallic Sn and (iii) metallic Pt. The formation of mixed Sn-Ce oxide is accompanied by partial reduction of Ce(4+) cations to Ce(3+). Pt deposition leads to the formation of Pt-Sn nanoalloys accompanied by the partial re-oxidation of Ce(3+) to Ce(4+). Subsequent annealing promotes further Pt-Sn alloy formation at expense of the Sn content in the Sn-Ce mixed oxide. Adsorption of H2 on Pt-Sn/Sn-Ce-O at 150 K followed by stepwise annealing results in reversible reduction of Ce cations caused by spillover of dissociated hydrogen between 150 and 300 K. Above 500 K, annealing of Pt-Sn/Sn-Ce-O in a hydrogen atmosphere results in irreversible reduction of Ce cations. This reduction is caused by the reaction of hydrogen with oxygen provided by the mixed oxide substrate via the reverse spillover to Pt-Sn nanoalloy. The extent of the hydrogen and oxygen spillover strongly depends on the amount of Sn in the Sn-Ce mixed-oxide. We observe an enhancement of hydrogen spillover on Pt-Sn/Sn-Ce-O at low Sn concentration as compared to Sn-free Pt/CeO2. Although the extent of hydrogen spillover on Pt-Sn/Sn-Ce-O with high Sn concentration is comparable to Pt/CeO2, the reverse oxygen spillover is substantially suppressed on these s les.
Publisher: Wiley
Date: 11-2083
Abstract: Towards a molecular understanding of the mechanism behind catalytic reforming of bioderived hydrocarbon oxygenates, we explore the C-C bond scission of C2 model compounds (acetic acid, ethanol, ethylene glycol) on ceria model catalysts of different complexity, with and without platinum. Synchrotron photoelectron spectroscopy reveals that the reaction pathway depends very specifically on both the reactant molecule and the catalyst surface. Whereas C-C bond scission on Pt sites and on oxygen vacancies involves intermittent surface carbon species, the reaction occurs without any carbon formation and deposition for ethylene glycol on CeO2(111).
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8TA08142E
Abstract: Metal-support interactions at the Pt/Co 3 O 4 (111) interface yield Pt δ+ species which control the stability of the supported nanoparticles.
Publisher: AIP Publishing
Date: 26-11-2019
DOI: 10.1063/1.5126031
Abstract: Iridium-based materials are among the most active bifunctional catalysts in heterogeneous catalysis and electrocatalysis. We have investigated the properties of atomically defined Ir/CeO2(111) model systems supported on Cu(111) and Ru(0001) by means of synchrotron radiation photoelectron spectroscopy, resonant photoemission spectroscopy, near ambient pressure X-ray photoelectron spectroscopy (NAP XPS), scanning tunneling microscopy, and temperature programmed desorption. Electronic metal-support interactions in the Ir/CeO2(111) system are accompanied by charge transfer and partial reduction of CeO2(111). The magnitude of the charge transfer depends strongly on the Ir coverage. The Ir/CeO2(111) system is stable against sintering upon annealing to 600 K in ultrahigh vacuum (UHV). Annealing of Ir/CeO2(111) in UHV triggers the reverse oxygen spillover above 450 K. The interaction of hydrogen with Ir/CeO2(111) involves hydrogen spillover and reversible spillover between 100 and 400 K accompanied by the formation of water above 190 K. Formation of water coupled with the strong reduction of CeO2(111) represents the dominant reaction channel upon annealing in H2 above 450 K. The interaction of Ir/CeO2(111) with oxygen has been investigated at moderate and NAP conditions. Additionally, the formation and stability of iridium oxide prepared by deposition of Ir in oxygen atmosphere was investigated upon annealing in UHV and under exposure to H2. The oxidation of Ir nanoparticles under NAP conditions yields stable IrOx nanoparticles. The stability of Ir and IrOx nanoparticles under oxidizing conditions is h ered, however, by encapsulation by cerium oxide above 450 K and additionally by copper and ruthenium oxides under NAP conditions.
Publisher: American Chemical Society (ACS)
Date: 29-05-2012
DOI: 10.1021/JP302229X
Publisher: American Chemical Society (ACS)
Date: 09-05-2018
DOI: 10.1021/ACS.JPCLETT.8B01033
Abstract: Understanding the correlation between structure and reactivity of oxide surfaces is vital for the rational design of catalytic materials. In this work, we demonstrate the exceptional degree of structure sensitivity of the water dissociation reaction for one of the most important materials in catalysis and electrocatalysis. We studied H
Publisher: Royal Society of Chemistry (RSC)
Date: 06-10-2014
DOI: 10.1039/C4CP03346A
Abstract: By means of synchrotron radiation photoemission spectroscopy, we have investigated Pt-CeO2 mixed oxide films prepared on CeO2(111)/Cu(111). Using CO molecules as a probe, we associate the corresponding surface species with specific surface sites. This allows us to identify the changes in the composition and morphology of Pt-CeO2 mixed oxide films caused by annealing in an ultrahigh vacuum. Specifically, two peaks in C 1s spectra at 289.4 and 291.2 eV, associated with tridentate and bidentate carbonate species, are formed on the nanostructured stoichiometric CeO2 film. The peak at 290.5-291.0 eV in the C 1s spectra indicates the onset of restructuring, i.e. coarsening, of the Pt-CeO2 film. This peak is associated with a carbonate species formed near an oxygen vacancy. The onset of cerium oxide reduction is indicated by the peak at 287.8-288.0 eV associated with carbonite species formed near Ce(3+) cations. The development of surface species on the Pt-CeO2 mixed oxides suggests that restructuring of the films occurs above 300 K irrespective of Pt loadings. We do not find any adsorbed CO species associated with Pt(4+) or Pt(2+). The onset of Pt(2+) reduction is indicated by the peak at 286.9 eV in the C 1s spectra due to CO adsorption on metallic Pt particles. The thermal stability of Pt(2+) in Pt-CeO2 mixed oxide depends on Pt loading. We find excellent stability of Pt(2+) for 12% Pt content in the CeO2 film, whereas at a Pt concentration of 25% in the CeO2 film, a large fraction of the Pt(2+) is converted into metallic Pt particles above 300 K.
Publisher: American Chemical Society (ACS)
Date: 11-04-2011
DOI: 10.1021/JP200382Y
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7TA02204B
Abstract: The concentration of Ce 3+ centers in Pt–CeO 2 films determines the onset of reduction of atomically dispersed platinum species.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C1CP22863C
Abstract: The catalytic activity of cerium dioxide can be modified by deposition of alkaline earth oxide layers or nanoparticles or by substitutional doping of metal cations at the Ce site in ceria. In order to understand the effect of Mg oxide deposition and doping, a combination of experiment and first principles simulations is a powerful tool. In this paper, we examine the interaction of Mg with the ceria (111) surface using both angle resolved X-ray (ARXPS) and resonant (RPES) photoelectron spectroscopy measurements and density functional theory (DFT) corrected for on-site Coulomb interactions (DFT + U). With DFT + U, we also examine the interaction of Mg with the ceria (110) surface. The experiments show that upon deposition of Mg, Ce ions are reduced to Ce(3+), while Mg is oxidised. When Mg is incorporated into ceria, no reduced Ce(3+) ions are found and oxygen vacancies are present. The DFT + U simulations show that each Mg that is introduced leads to formation of two reduced Ce(3+) ions. When Mg is incorporated at a Ce site in the (111) surface, one oxygen vacancy is formed for each Mg to compensate the different valencies, so that all Ce ions are oxidised. The behaviour of Mg upon interaction with the (110) surface is the same as with the (111) surface. The combined results provide a basis for deeper insights into the catalytic behaviour of ceria-based mixed oxide catalysts.
Publisher: American Chemical Society (ACS)
Date: 16-03-2023
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0CP05606E
Abstract: The metastability of the Pd 6 C phase results from the thermodynamically favorable growth of graphene.
Publisher: American Chemical Society (ACS)
Date: 25-09-2019
DOI: 10.1021/ACS.JPCLETT.9B02398
Abstract: Quantitative assessment of the charge transfer phenomena in cobalt oxides and cobalt complexes is essential for the design of advanced catalytic materials. We propose a method for the evaluation of the oxidation state of cobalt oxides with mixed valence states using resonant photoemission spectroscopy. The method is based on the calculation of the resonant enhancement ratio (RER) from the heights of the resonant features associated with the Co
Publisher: American Chemical Society (ACS)
Date: 24-06-2014
DOI: 10.1021/JP502017T
Publisher: American Chemical Society (ACS)
Date: 19-09-2011
DOI: 10.1021/JP207014Z
No related grants have been discovered for Yaroslava Lykhach.