CO Oxidation on Planar Au/TiO2_{2} Model Catalysts under Realistic Conditions: A Combined Kinetic and IR Study

The oxidation of CO on planar Au/TiO$_{2}$ model catalysts was investigated under pressure and temperature conditions similar to those for experiments with more realistic Au/TiO$_{2}$ powder catalysts. The effects of a change of temperature, pressure, and gold coverage on the CO oxidation activity were studied. Additionally, the reasons for the deactivation of the catalysts were examined in long‐term experiments. From kinetic measurements, the activation energy and the reaction order for the CO oxidation reaction were derived and a close correspondence with results of powder catalysts was found, although the overall turnover frequency (TOF) measured in our experiments was around one order of magnitude lower compared to results of powder catalysts under similar conditions. Furthermore, long‐term experiments at 80 °C showed a decrease of the activity of the model catalysts after some hours. Simultaneous in‐situ IR experiments revealed a decrease of the signal intensity of the CO vibration band, while the tendency for the build‐up of side products (e. g. carbonates, carboxylates) of the CO oxidation reaction on the surface of the planar model catalysts was rather low

Model Studies on the Formation of the Solid Electrolyte Interphase: Reaction of Li with Ultrathin Adsorbed Ionic-Liquid Films and Co3_{3}O4_{4}(111) Thin Films

In this work we aim towards the molecular understanding of the solid electrolyte interphase (SEI) formation at the electrode electrolyte interface (EEI). Herein, we investigated the interaction between the battery‐relevant ionic liquid (IL) 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP‐TFSI), Li and a Co$_{3}$O$_{4}$(111) thin film model anode grown on Ir(100) as a model study of the SEI formation in Li‐ion batteries (LIBs). We employed mostly X‐ray photoelectron spectroscopy (XPS) in combination with dispersion‐corrected density functional theory calculations (DFT‐D3). If the surface is pre‐covered by BMP‐TFSI species (model electrolyte), post‐deposition of Li (Li$^{+}$ ion shuttle) reveals thermodynamically favorable TFSI decomposition products such as LiCN, Li$_{2}$NSO$_{2}$CF$_{3}$, LiF, Li$_{2}$S, Li$_{2}$O$_{2}$, Li$_{2}$O, but also kinetic products like Li$_{2}$NCH$_{3}$C$_{4}$H$_{9}$ or LiNCH$_{3}$C$_{4}$H$_{9}$ of BMP. Simultaneously, Li adsorption and/or lithiation of Co$_{3}$O$_{4}$(111) to LinCo$_{3}$O$_{4}$ takes place due to insertion via step edges or defects; a partial transformation to CoO cannot be excluded. Formation of Co$^{0}$ could not be observed in the experiment indicating that surface reaction products and inserted/adsorbed Li at the step edges may inhibit or slow down further Li diffusion into the bulk. This study provides detailed insights of the SEI formation at the EEI, which might be crucial for the improvement of future batteries

Fundamental Aspects of Ceria Supported Au Catalysts Probed by In Situ/Operando Spectroscopy and TAP Reactor Studies

The discovery of the activity of dispersed gold nanoparticles three decades ago paved the way for a new era in catalysis. The unusual behavior of these catalysts sparked many questions about their working mechanism. In particular, Au/CeO2 proved to be an efficient catalyst in several reactions such as CO oxidation, water gas shift, and CO2 reduction. Here, by employing findings from operando X-ray absorption spectroscopy at the near and extended Au and Ce LIII energy edges, we focus on the fundamental aspects of highly active Au/CeO2 catalysts, mainly in the CO oxidation for understanding their complex structure-reactivity relationship. These results were combined with findings from in situ diffuse reflectance FTIR and Raman spectroscopy, highlighting the changes of adlayer and ceria defects. For a comprehensive understanding, the spectroscopic findings will be supplemented by results of the dynamics of O2 activation obtained from Temporal Analysis of Products (TAP). Merging these results illuminates the complex relationship among the oxidation state, size of the Au nanoparticles, the redox properties of CeO2 support, and the dynamics of O2 activation

Unveiling the CO Oxidation Mechanism over a Molecularly Defined Copper Single-Atom Catalyst Supported on a Metal-Organic Framework

Elucidating the reaction mechanism in heterogeneous catalysis is critically important for catalyst development, yet remains challenging because of the often unclear nature of the active sites. Using a molecularly defined copper single-atom catalyst supported by a UiO-66 metal-organic framework (Cu/UiO-66) allows a detailed mechanistic elucidation of the CO oxidation reaction. Based on a combination of in situ/operando spectroscopies, kinetic measurements including kinetic isotope effects, and density-functional-theory-based calculations, we identified the active site, reaction intermediates, and transition states of the dominant reaction cycle as well as the changes in oxidation/spin state during reaction. The reaction involves the continuous reactive dissociation of adsorbed O2 , by reaction of O2,ad with COad , leading to the formation of an O atom connecting the Cu center with a neighboring Zr4+ ion as the rate limiting step. This is removed in a second activated step

Enhanced Electrochemical Capacity of Spherical Co-Free Li1.2_{1.2}Mn0.6_{0.6}Ni0.2_{0.2}O2_{2} Particles after a Water and Acid Treatment and its Influence on the Initial Gas Evolution Behavior

Li-rich layered oxides (LRLO) with specific energies beyond 900 Wh kg$^{−1}$ are one promising class of high-energy cathode materials. Their high Mn-content allows reducing both costs and the environmental footprint. In this work, Co-free Li$_{1.2}$Mn$_{0.6}$Ni$_{0.2}$O$_{2}$ was investigated. A simple water and acid treatment step followed by a thermal treatment was applied to the LRLO to reduce surface impurities and to establish an artificial cathode electrolyte interface. Samples treated at 300 °C show an improved cycling behavior with specific first cycle capacities of up to 272 mAh g$^{−1}$, whereas powders treated at 900 °C were electrochemically deactivated due to major structural changes of the active compounds. Surface sensitive analytical methods were used to characterize the structural and chemical changes compared to the bulk material. Online DEMS measurements were conducted to get a deeper understanding of the effect of the treatment strategy on O$_2$ and CO$_2$ evolution during electrochemical cycling

Reversible growth of gold nanoparticles in the low-temperature water-gas shift reaction

Supported gold nanoparticles are widely studied catalysts and are among the most active known for the low-temperature water–gas shift reaction, which is essential in fuel and energy applications, but their practical application has been limited by their poor thermal stability. The catalysts deactivate on-stream via the growth of small Au nanoparticles. Using operando X-ray absorption and in situ scanning transmission electron microscopy, we report direct evidence that this process can be reversed by carrying out a facile oxidative treatment, which redisperses the gold nanoparticles and restores catalytic activity. The use of in situ methods reveals the complex dynamics of supported gold nanoparticles under reaction conditions and demonstrates that gold catalysts can be easily regenerated, expanding their scope for practical application

Ein kleines oekonometrisches Makromodell fuer die Bundesrepublik Deutschland

Available from Bibliothek des Instituts fuer Weltwirtschaft, ZBW, Duesternbrook Weg 120, D-24105 Kiel C 147156 / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekSIGLEDEGerman

Structure, morphology, and magnetic properties of Fe nanoparticles deposited onto single-crystalline surfaces

Background: Magnetic nanostructures and nanoparticles often show novel magnetic phenomena not known from the respective bulk materials. In the past, several methods to prepare such structures have been developed – ranging from wet chemistry-based to physical-based methods such as self-organization or cluster growth. The preparation method has a significant influence on the resulting properties of the generated nanostructures. Taking chemical approaches, this influence may arise from the chemical environment, reaction kinetics and the preparation route. Taking physical approaches, the thermodynamics and the kinetics of the growth mode or – when depositing preformed clusters/nanoparticles on a surface – the landing kinetics and subsequent relaxation processes have a strong impact and thus need to be considered when attempting to control magnetic and structural properties of supported clusters or nanoparticles

Direct Observation of Magnetic Metastability in Individual Iron Nanoparticles

X-ray photoemission electron microscopy combined with x-ray magnetic circular dichroism is used to study the magnetic properties of individual iron nanoparticles with sizes ranging from 20 down to 8 nm. While the magnetocrystalline anisotropy of bulk iron suggests superparamagnetic behavior in this size range, ferromagnetically blocked particles are also found at all sizes. Spontaneous transitions from the blocked state to the superparamagnetic state are observed in single particles and suggest that the enhanced magnetic energy barriers in the ferromagnetic particles are due to metastable, structurally excited states with unexpected life time

A combined XPS and computational study of the chemical reduction of BMP-TFSI by lithium

Employing density functional theory (DFT) calculations and x-ray photoelectron spectroscopy (XPS), we identify products of the reaction of the ionic liquid N,N - butylmethylpyrrolidinum bis(trifluoromethylsulfonyl)imide (BMP-TFSI) with lithium in order to model the initial chemical processes contributing to the formation of the solid electrolyte interphase in batteries. Besides lithium oxide, sulfide, carbide and fluoride, we find lithium cyanide or cyanamide as possible, thermodynamically stable products in the Li-poor regime, whilst Li3N is the stable product in the Li-rich regime. The thermodynamically controlled reaction products as well as larger fragments of TFSI persisting due to kinetic barriers could be identified by a comparison of experimentally and computationally determined core level binding energies