Transition from a molecular to a metallic adsorbate system: Core-hole creation and decay dynamics for CO coordinated to Pd

Two alternative methods to experimentally monitor the development of a CO-adsorption system that gradually changes from molecular to metallic are presented: firstly by adsorption of CO on Pd islands of increasing size deposited under UHV conditions, and secondly by growth of a Pd carbonyl-like species, formed by Pd deposition in CO atmosphere. The change in screening dynamics as a function of the number of metal atoms was investigated, using x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and core-hole-decay techniques. For CO adsorbed on UHV-deposited islands, the electronic properties of the whole CO-Pd complex is strongly dependent on island size and CO coverage: large amounts of CO result in a reduced screening ability, and small effects characteristic of molecular systems can be detected even for islands containing about 100 Pd atoms. If about half of the CO overlayer is desorbed, the CO-Pd complex exhibits a relaxation upon core ionization that is nearly as efficient as for metallic systems, even for the smallest islands (of the order of 10 Pd atoms). The growth of the carbonyl-like compound proceeds via formation of Pd-Pd bonds and has a relatively well-defined local structure. It is demonstrated that the properties of this compound approach those of an extended system for increasing coverages, and it may therefore also serve as an important link between a carbonyl and CO adsorbed on a metallic surface. A brief discussion is also given in which the results are discussed in terms of electronic properties of the thin alumina film versus bulk alumina and the applicability of the former to the construction of model catalysts

Interaction of CO with Pd clusters supported on a thin alumina film

The adsorption of CO on Pd particles supported on a thin alumina film has been studied employing high resolution x‐ray photoelectron spectroscopy (XPS) and x‐ray absorption spectroscopy (XAS), and of special interest was the CO–Pd interaction as a function of island size and CO coverage. CO saturation at 90 K leads to an overlayer characterized by a rather weak CO–Pd hybridization as manifested by the core ionized and core excited states. The interaction strength gradually increases with island size. Desorption of parts of the overlayer results in CO more strongly interacting with the Pd islands. A comparison between the XPS and XAS energies yields a behavior indistinguishable from metallic systems for islands larger than 15 Å, i.e., the XPS binding energy appears near the x‐ray absorption onset. For the smallest islands (5 Å), a CO coverage dependent reversal of the XPS–XAS energy relation was observed, indicating a drastic change in the screening ability of the CO–Pd complex

Set-up of a novel Electrochemical IR Spectroscopy Apparatus with Liquid/Solid-Interface-Preparation: ELISA I&II

Pt-doped CeO2 has been identified as a potential anode electrocatalyst in proton exchange membrane fuel cells (PEMFC). Providing very high noble metal efficiency, the material may help to decrease the demand for Pt, while simultaneously increasing the tolerance against CO poisoning. To investigate complex model catalysts\u2019 surfaces on single crystals under ultraclean conditions the latter must be prepared in the ultrahigh vacuum (UHV). To this end we present a UHV system that allows preparation and characterization of model electrocatalysts and subsequent transfer to an electrochemical cell without contact to ambient atmosphere. The system is equipped with all standard preparations tools, electron beam evaporators, thermal evaporator cells and a quartz microbalance. Structural and chemical analysis is possible by low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and temperature programmed desorption (TPD). The sample single crystal is transferred through a differentially pumped stage into the electrolyte without breaking the UHV in the preparation system. Contamination-free transfer of the prepared single crystal samples are characterized by cyclic voltammetry (CV). To explore the chemical state of the Pt species in the ceria matrix under reaction conditions we apply insitu electrochemical IR spectroscopy. Towards this aim we have set up a new IR spectroelectrochemistry system that includes a state-of-the-art vacuum FTIR spectrometer and an optimized external reflection cell. We demonstrate that the system is functional and provides an excellent signal/noise ratio

Norbornadiene photoswitches anchored to well-defined oxide surfaces: From ultrahigh vacuum into the liquid and the electrochemical environment

Employing molecular photoswitches, we can combine solar energy conversion, storage, and release in an extremely simple single molecule system. In order to release the stored energy as electricity, the photoswitch has to interact with a semiconducting electrode surface. In this work, we explore a solar-energy-storing model system, consisting of a molecular photoswitch anchored to an atomically defined oxide surface in a liquid electrolyte and under potential control. Previously, this model system has been proven to be operational under ultrahigh vacuum (UHV) conditions. We used the tailor-made norbornadiene derivative 2-cyano-3-(4-carboxyphenyl)norbornadiene (CNBD) and characterized its photochemical and electrochemical properties in an organic electrolyte. Next, we assembled a monolayer of CNBD on a well-ordered Co3O4(111) surface by physical vapor deposition in UHV. This model interface was then transferred into the liquid electrolyte and investigated by photoelectrochemical infrared reflection absorption spectroscopy experiments. We demonstrate that the anchored monolayer of CNBD can be converted photochemically to its energy-rich counterpart 2-cyano-3-(4-carboxyphenyl)quadricyclane (CQC) under potential control. However, the reconversion potential of anchored CQC overlaps with the oxidation and decomposition potential of CNBD, which limits the electrochemically triggered reconversion

SOx storage and release kinetics for ceria-supported Pt

The SOx storage and release kinetics on CeO2 have been studied by lean SOx adsorption and temperature programmed desorption for different pairwise configurations of individual monolith samples, i.e., Pt/CeO2 + SiO2, Pt/SiO2 + CeO2, CeO2 + Pt/SiO2 and CeO2 + SiO2. In the case of sole ceria, SOx adsorption proceeds both via SO2 and SO3 adsorption although the latter channel is kinetically favored. Hence, the rate of SO2 oxidation is crucial for the overall SOx storage kinetics. It is also found that physical contact between Pt and ceria is important for the storage process. This is attributed to efficient transport routes for SOx (surface diffusion and spill-over processes) and/or specific adsorption sites at the platinum–ceria interface. The main route for SOx release is found to be thermal decomposition where the effect of platinum is minor, although an indirect effect cannot be ruled out. Different mechanistic scenarios for SOx adsorption are discussed, which may serve as a guide for future experiments

Towards an efficient liquid organic hydrogen carrier fuel cell concept

The high temperature required for hydrogen release from Liquid Organic Hydrogen Carrier (LOHC) systems has been considered in the past as the main drawback of this otherwise highly attractive and fully infrastructure-compatible form of chemical hydrogen storage. According to the state-of-the art, the production of electrical energy from LOHC-bound hydrogen, e.g. from perhydro-dibenzyltoluene (H18DBT), requires provision of the dehydrogenation enthalpy (e.g. 65 kJ mol-1(H2) for H18-DBT) at a temperature level of 300 °C followed by purification of the released hydrogen for subsequent fuel cell operation. Here, we demonstrate that a combination of a heterogeneously catalysed transfer hydrogenation from H18-DBT to acetone and fuel cell operation with the resulting 2-propanol as a fuel, allows for an electrification of LOHC-bound hydrogen in high efficiency (> 50 %) and at surprisingly mild conditions (temperatures below 200 °C). Most importantly, our proposed new sequence does not require an external heat input as the transfer hydrogenation from H18-DBT to acetone is almost thermoneutral. In the PEMFC operation with 2-propanol, the endothermal proton release at the anode is compensated by the exothermic formation of water. Ideally the proposed sequence does not form and consume molecular H2 at any point which adds a very appealing safety feature to this way of producing electricity from LOHC-bound hydrogen, e.g. for applications on mobile platforms.Fil: Sievi, Gabriel. Forschungszentrum Jülich; AlemaniaFil: Geburtig, Denise. Universitat Erlangen-Nuremberg; AlemaniaFil: Skeledzic, Tanja. Forschungszentrum Jülich; AlemaniaFil: Bösmann, Andreas. Universitat Erlangen-Nuremberg; AlemaniaFil: Preuster, Patrick. Forschungszentrum Jülich; AlemaniaFil: Brummel, Olaf. Universitat Erlangen-Nuremberg; AlemaniaFil: Waidhas, Fabian. Universitat Erlangen-Nuremberg; AlemaniaFil: Montero, María de Los Angeles. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; ArgentinaFil: Khanipour, Peyman. Forschungszentrum Jülich; AlemaniaFil: Katsounaros, Ioannis. Forschungszentrum Jülich; AlemaniaFil: Libuda, Jörg. Universitat Erlangen-Nuremberg; AlemaniaFil: Mayrhofer, Karl J. J.. Forschungszentrum Jülich; AndorraFil: Wasserscheid, Peter. Universitat Erlangen-Nuremberg; Alemani

Metal-support interaction and charge distribution in ceria-supported Au particles exposed to CO

Understanding how reaction conditions affect metal-support interactions in catalytic materials is one of the most challenging tasks in heterogeneous catalysis research. Metal nanoparticles and their supports often undergo changes in structure and oxidation state when exposed to reactants, hindering a straightforward understanding of the structure-activity relations using only ex situ or ultrahigh vacuum techniques. Overcoming these limitations, we explored the metal-support interaction between gold nanoparticles and ceria supports in ultrahigh vacuum and after exposure to CO. A combination of in situ methods (on powder and model Au/CeO2 samples) and theoretical calculations was applied to investigate the gold/ceria interface and its reactivity toward CO exposure. X-ray photoelectron spectroscopy measurements rationalized by first-principles calculations reveal a distinctly inhomogeneous charge distribution, with Au+ atoms in contact with the ceria substrate and neutral Au0 atoms at the surface of the Au nanoparticles. Exposure to CO partially reduces the ceria substrate, leading to electron transfer to the supported Au nanoparticles. Transferred electrons can delocalize among the neutral Au atoms of the particle or contribute to forming inert Auδ− atoms near oxygen vacancies at the ceria surface. This charge redistribution is consistent with the evolution of the vibrational frequencies of CO adsorbed on Au particles obtained using diffuse reflectance infrared Fourier transform spectroscopy