Studium katalyzátorů Pt-CeO2 připravených magnetonovým naprašováním

Title: Investigation of magnetron sputtered Pt-CeO2 thin film catalyst for fuel cell applications. Author: Mgr. Mykhailo Vorokhta Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. [email protected] Abstract: This doctoral thesis focuses on magnetron sputtered Pt-doped CeO2 thin films that were found to be very active catalysts in proton exchange membrane fuel cells (PEMFC). The films were prepared on different substrates (silicon wafers, carbon nanotubes and flat carbon substrates) and investigated mainly by means of Hard x-ray photoelectron spectroscopy (HAXPES). The HAXPES method showed that deposition of the Pt doped cerium oxide catalyst layers on carbon nanotubes and flat carbon substrates by magnetron sputtering leads to growth of a highly porous "Pt-Ce-O" solid solution film, where platinum is mostly in ionic states, Pt2+ , Pt4+ . The results obtained showed that the mechanism of film growth is strongly influenced by interaction of the Ce atoms with the substrate and their oxidation by oxygen containing RF plasma. The formation of Ptn+ states together with the porous character of the catalyst films are used to explain the high activity of Pt-CeO2 catalyst in PEMFCs. Keywords: magnetron sputtering, cerium oxide, Pt, XPS, SRPES.Název práce: Studium katalyzátorů Pt-CeO2 připravených magnetonovým naprašováním. Autor: Mgr. Mykhailo Vorokhta Katedra / Ústav: Katedra fyziky povrchů a plazmatu Vedoucí doktorské práce: Prof. RNDr. Vladimír Matolín, DrSc. [email protected] Abstrakt: Doktorská práce se zabývá studiem Pt dopovaných tenkých vrstev CeO2 připravených magnetronovým naprašováním, u kterých bylo zjištěno, že představují velice aktivní katalyzátor pro palivové články s proton-vodivou membránou (PEMFC). Tenké vrstvy Pt- CeO2 byly naprašovány na různé substráty (křemíkové a uhlíkové substráty, uhlíkové nanotrubky) a byly zkoumány převážně pomocí fotoelektronové spektroskopie buzené tvrdým rentgenovým zářením (HAXPES). Výsledky získané metodou HAXPES ukázaly, že příprava katalytických vrstev oxidu ceru dopovaných Pt na různých uhlíkových substrátech a nanotrubkách metodou magnetronového naprašování vede k růstu vysoce porézních vrstev Pt- Ce-O s platinou v iontovém stavu Pt2+ , Pt4+ . Získané výsledky také ukázaly, že mechanismus růstu vrstvy Pt-CeO2 je silně ovlivněn interakcí atomů Ce se substrátem a jejich oxidací v kyslíkovém plazmatu. Vznik Ptn+ stavů společně s porézním charakterem katalytických vrstev slouží k vysvětlení vysoké aktivity katalyzátorů na bázi Pt-CeO2 pro palivové články PEMFCs. Klíčová slova:...Katedra fyziky povrchů a plazmatuDepartment of Surface and Plasma ScienceFaculty of Mathematics and PhysicsMatematicko-fyzikální fakult

Structural transformations and adsorption properties of PtNi nanoalloy thin film electrocatalysts prepared by magnetron co-sputtering

This is the final peer-reviewed manuscript accepted for publication in Electrochimica Acta Citation of the published version is: Electrochimica Acta 251, 427–441 (2017

Adsorption structure of adenine on cerium oxide

The adsorption of adenine on the CeO2(1 1 1)/Cu(1 1 1) surface in vacuum was studied by photoelectron spectroscopy, resonant photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy, and the present work describes in detail the bonding of the molecule to the ordered stoichiometric cerium dioxide film. The experimental findings were supported by density functional theory (DFT + U) analysis of different adsorption geometries of adenine on CeO2(1 1 1). The phase with adenine lying flat on the surface dominates on CeO2(1 1 1) up to 0.1 monolayer (ML) of adenine coverage. The mobility of single molecules was apparently sufficiently high to allow diffusion and formation of chain structures, which were observed to be stable in the temperature range from 25 to 250 °C. Beyond 0.1 ML, adenine molecules adsorb predominantly in an upright orientation. This phase, stable up to 120 °C, is according to theory stabilised via N3/Ce4+ and N9H/O2–. It was further complemented by experimental findings demonstrating free N10H2 groups in adsorbed molecules. Thus, the saturation coverage of adenine on CeO2(1 1 1), 0.23 ML, is most likely characterised by a combination of parallel and upright bound molecules

Surface Composition of a Highly Active Pt3Y Alloy Catalyst for Application in Low Temperature Fuel Cells

Currently, platinum is the most widely used catalyst for low temperature proton exchange membrane fuel cells (PEMFC). However, the kinetics at the cathode are slow, and the price of platinum is high. To improve oxygen reduction reaction (ORR) kinetics at the cathode, platinum can be alloyed with rare earth elements, such as yttrium. We report that Pt3Y has the potential to be over 2 times more active for the ORR compared with Pt inside a real fuel cell. We present detailed photoemission analysis into the nature of the sputtered catalyst surface, using synchrotron radiation photoelectron spectroscopy (SRPES) to examine if surface adsorbates or impurities are present and can be removed. Pretreatment removes most of the yttrium oxide in the surface leaving behind a Pt overlayer which is only a few monolayers thick. Evidence of a substochiometric oxide peak in the Y 3d core level is presented, this oxide extends into the surface even after Ar+ sputter cleaning in-situ. This information will aid the development of new highly active nanocatalysts for employment in real fuel cell electrodes

Hydrogen activation on Pt–Sn nanoalloys supported on mixed Sn–Ce oxide films

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 Ce4+ cations to Ce3+. Pt deposition leads to the formation of Pt–Sn nanoalloys accompanied by the partial re-oxidation of Ce3+ to Ce4+. 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 samples

Surface sites on Pt–CeO2 mixed oxide catalysts probed by CO adsorption: a synchrotron radiation photoelectron spectroscopy study

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 Ce3+ 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 Pt4+ or Pt2+. The onset of Pt2+ 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 Pt2+ in Pt–CeO2 mixed oxide depends on Pt loading. We find excellent stability of Pt2+ for 12% Pt content in the CeO2 film, whereas at a Pt concentration of 25% in the CeO2 film, a large fraction of the Pt2+ is converted into metallic Pt particles above 300 K

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-Enabled Catalytic Conversion by Site Blocking

[EN] The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH → CHOH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy and density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. These findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.The work carried out at Brookhaven National Laboratory was supported by the U.S. Department of Energy (Chemical Sciences Division, DE-SC0012704). S.D.S. is supported by a U.S. Department of Energy Early Career Award. This research used resources of the Advanced Light Source (Beamline 9.3.2),which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Authors acknowledge contribution of Dr. Ethan Crumlin for assistance with AP-XPS measurements. M.V.G.-P. acknowledges the financial support of the /Ministry of Economy and Competitiveness MINECO-Spain (Grant No. CTQ2015-78823-R) and P.G.L. that of the Agencia Nacional de Promocion Científiica y Tecnologica-Argentina (Grant No. PICT-2016-2750). Computer time provided by the BIFI-ZCAM, RES at the Marenostrum and La Palma nodes, SNCAD (Sistema Nacional de Computación de Alto Desempeño, Argentina), and the DECI resources BEM based in Poland at WCSS and Archer at EPCC with support from the PRACE aislb, is acknowledged. M.V. thanks the Ministry of Education, Youth and Sports of the Czech Republic for financial support under Project LH15277. R.M.P. was partially funded by the AGEP-T (Alliance for Graduate Education and the Professoriate−Transformation) which is funded by the National Science Foundation, award #131131

In situ probing of Pt/TiO2_{2} activity in low-temperature ammonia oxidation

The improvement of the low-temperature activity of the supported platinum catalysts in selective ammonia oxidation to nitrogen is still a challenging task. The recent developments in in situ/operando characterization techniques allows to bring new insight into the properties of the systems in correlation with their catalytic activity. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando X-ray absorption spectroscopy (XAS) techniques were applied to study Pt/TiO$_{2}$ catalysts in ammonia oxidation (NH$_{3}$ + O$_{2}$ reaction). Several synthesis methods were used to obtain samples with different size of Pt particles, oxidation state of Pt, and morphology of the support. Metal platinum particles on titania prepared by pulsed laser ablation in liquids exhibited the highest activity at lower temperatures with the temperature of 50% conversion of NH$_{3}$ being 150 °C. The low-temperature activity of the catalysts synthesized by impregnation can be improved by the reductive pretreatment. NAP-XPS and operando XANES data do not show formation of PtO$_{x}$ surface layers or PtO/PtO$_{2}$ oxides during NH$_{3}$ + O$_{2}$ reaction. Despite the differences in the oxidation state of platinum in the as-prepared catalysts, their treatment in the reaction mixture results in the formation of metallic platinum particles, which can serve as centers for stabilization of the adsorbed oxygen species. Stabilization of the bulk platinum oxide structures in the Pt/TiO$_{2}$ catalysts seems to be less favorable due to the metal–support interaction

Reactivity of atomically dispersed Pt2+ species towards H2: model Pt–CeO2 fuel cell catalyst

The reactivity of atomically dispersed Pt2+ species on the surface of nanostructured CeO2 films and the mechanism of H2 activation on these sites have been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy in combination with density functional calculations. Isolated Pt2+ sites are found to be inactive towards H2 dissociation due to high activation energy required for H–H bond scission. Trace amounts of metallic Pt are necessary to initiate H2 dissociation on Pt–CeO2 films. H2 dissociation triggers the reduction of Ce4+ cations which, in turn, is coupled with the reduction of Pt2+ species. The mechanism of Pt2+ reduction involves reverse oxygen spillover and formation of oxygen vacancies on Pt–CeO2 films. Our calculations suggest the existence of a threshold concentration of oxygen vacancies associated with the onset of Pt2+ reduction

Investigation of magnetron sputtered Pt-CeO2 thin film catalyst for fuel cell applications

Title: Investigation of magnetron sputtered Pt-CeO2 thin film catalyst for fuel cell applications. Author: Mgr. Mykhailo Vorokhta Department: Department of Surface and Plasma Science Supervisor: Prof. RNDr. Vladimír Matolín, DrSc. [email protected] Abstract: This doctoral thesis focuses on magnetron sputtered Pt-doped CeO2 thin films that were found to be very active catalysts in proton exchange membrane fuel cells (PEMFC). The films were prepared on different substrates (silicon wafers, carbon nanotubes and flat carbon substrates) and investigated mainly by means of Hard x-ray photoelectron spectroscopy (HAXPES). The HAXPES method showed that deposition of the Pt doped cerium oxide catalyst layers on carbon nanotubes and flat carbon substrates by magnetron sputtering leads to growth of a highly porous "Pt-Ce-O" solid solution film, where platinum is mostly in ionic states, Pt2+ , Pt4+ . The results obtained showed that the mechanism of film growth is strongly influenced by interaction of the Ce atoms with the substrate and their oxidation by oxygen containing RF plasma. The formation of Ptn+ states together with the porous character of the catalyst films are used to explain the high activity of Pt-CeO2 catalyst in PEMFCs. Keywords: magnetron sputtering, cerium oxide, Pt, XPS, SRPES