Titanium Oxycarbide as Platinum-Free Electrocatalyst for Ethanol Oxidation.

The compound material titanium oxycarbide (TiOC) is found to be an effective electrocatalyst for the electrochemical oxidation of ethanol to CO2. The complete course of this reaction is one of the main challenges in direct ethanol fuel cells (DEFCs). While TiOC has previously been investigated as catalyst support material only, in this study we show that TiOC alone is able to oxidize ethanol to acetaldehyde without the need of expensive noble metal catalysts like Pt. It is suggested that this behavior is attributed to the presence of both undercoordinated sites, which allow ethanol to adsorb, and oxygenated sites, which facilitate the activation of water. This is a milestone in DEFC research and development and opens up innovative possibilities for the design of catalyst materials for intermediate temperature fuel cells.

A laboratory-based multifunctional near ambient pressure X-ray photoelectron spectroscopy system for electrochemical, catalytic, and cryogenic studies.

A versatile multifunctional laboratory-based near ambient pressure x-ray photoelectron spectroscopy (XPS) instrument is presented. The entire device is highly customized regarding geometry, exchangeable manipulators and sample stages for liquid- and solid-state electrochemistry, cryochemistry, and heterogeneous catalysis. It therefore delivers novel and unique access to a variety of experimental approaches toward a broad choice of functional materials and their specific surface processes. The high-temperature (electro)catalysis manipulator is designed for probing solid state/gas phase interactions for heterogeneous catalysts including solid electrolyzer/fuel cell electrocatalysts at pressures up to 15 mbar and temperatures from room temperature to 1000 °C. The liquid electrochemistry manipulator is specifically designed for in situ spectroscopic investigations of polarized solid/liquid interfaces using aqueous electrolytes and the third one for experiments for ice and ice-like materials at cryogenic temperatures to approximately -190 °C. The flexible and modular combination of these setups provides the opportunity to address a broad spectrum of in situ and operando XPS experiments on a laboratory-based system, circumventing the limited accessibility of experiments at synchrotron facilities.

Zirconium Carbide Mediates Coke-Resistant Methane Dry Reforming on Nickel-Zirconium Catalysts.

Graphitic deposits anti-segregate into Ni0 nanoparticles to provide restored CH4 adsorption sites and near-surface/dissolved C atoms, which migrate to the Ni0 /ZrO2 interface and induce local Zrx Cy formation. The resulting oxygen-deficient carbidic phase boundary sites assist in the kinetically enhanced CO2 activation toward CO(g). This interface carbide mechanism allows for enhanced spillover of carbon to the ZrO2 support, and represents an alternative catalyst regeneration pathway with respect to the reverse oxygen spillover on Ni-CeZrx Oy catalysts. It is therefore rather likely on supports with limited oxygen storage/exchange kinetics but significant carbothermal reducibility.

Porous Silicon Oxycarbonitride Ceramics with Palladium and Pd2Si Nanoparticles for Dry Reforming of Methane.

Pd-containing precursor has been synthesized from palladium acetate and poly(vinly)silazane (Durazane 1800) in an ice bath under an argon atmosphere. The results of ATR-FTIR and NMR characterizations reveal the chemical reaction between palladium acetate and vinyl groups in poly(vinyl)silazane and the hydrolyzation reaction between -Si-H and -Si-CH=CH2 groups in poly(vinyl)silazane. The palladium nanoparticles are in situ formed in the synthesized precursors as confirmed by XRD, XPS, and TEM. Pd- and Pd2Si-containing SiOCN ceramic nanocomposites are obtained by pyrolysis of the synthesized precursors at 700 °C, 900 °C-1100 °C in an argon atmosphere. The pyrolyzed nanocomposites display good catalytic activity towards the dry reforming of methane. The sample pyrolyzed at 700 °C possesses the best catalytic performance, which can be attributed to the in situ formed palladium nanoparticles and high BET surface area of about 233 m2 g-1.

Who Does the Job? How Copper Can Replace Noble Metals in Sustainable Catalysis by the Formation of Copper-Mixed Oxide Interfaces.

Following the need for an innovative catalyst and material design in catalysis, we provide a comparative approach using pure and Pd-doped LaCu x Mn1-x O3 (x = 0.3 and 0.5) perovskite catalysts to elucidate the beneficial role of the Cu/perovskite and the promoting effect of Cu y Pd x /perovskite interfaces developing in situ under model NO + CO reaction conditions. The observed bifunctional synergism in terms of activity and N2 selectivity is essentially attributed to an oxygen-deficient perovskite interface, which provides efficient NO activation sites in contact with in situ exsolved surface-bound monometallic Cu and bimetallic CuPd nanoparticles. The latter promotes the decomposition of the intermediate N2O at low temperatures, enhancing the selectivity toward N2. We show that the intelligent Cu/perovskite interfacial design is the prerequisite to effectively replace noble metals by catalytically equally potent metal-mixed-oxide interfaces. We have provided the proof of principle for the NO + CO test reaction but anticipate the extension to a universal concept applicable to similar materials and reactions.

Properties of Bulk In-Pt Intermetallic Compounds in Methanol Steam Reforming.

Heterogeneous catalysts are often complex materials containing different compounds. While this can lead to highly beneficial interfaces, it is difficult to identify the role of single components. In methanol steam reforming (MSR), the interplay between intermetallic compounds, supporting oxides and redox reactions leads to highly active and CO2 -selective materials. Herein, the intrinsic catalytic properties of unsupported In3 Pt2 , In2 Pt, and In7 Pt3 as model systems for Pt/In2 O3 -based catalytic materials in MSR are addressed. In2 Pt was identified as the essential compound responsible for the reported excellent CO2 -selectivity of 99.5 % at 300 °C in supported systems, showing a CO2 -selectivity above 99 % even at 400 °C. Additionally, the partial oxidation of In7 Pt3 revealed that too much In2 O3 is detrimental for the catalytic properties. The study highlights the crucial role of intermetallic In-Pt compounds in Pt/In2 O3 materials with excellent CO2 -selectivity.

Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts.

To elucidate the role of earth alkaline doping in perovskite-based dry reforming of methane (DRM) catalysts, we embarked on a comparative and exemplary study of a Ni-based Sm perovskite with and without Sr doping. While the Sr-doped material appears as a structure-pure Sm1.5Sr0.5NiO4 Ruddlesden Popper structure, the undoped material is a NiO/monoclinic Sm2O3 composite. Hydrogen pre-reduction or direct activation in the DRM mixture in all cases yields either active Ni/Sm2O3 or Ni/Sm2O3/SrCO3 materials, with albeit different short-term stability and deactivation behavior. The much smaller Ni particle size after hydrogen reduction of Sm1.5Sr0.5NiO4, and of generally all undoped materials stabilizes the short and long-term DRM activity. Carbon dioxide reactivity manifests itself in the direct formation of SrCO3 in the case of Sm1.5Sr0.5NiO4, which is dominant at high temperatures. For Sm1.5Sr0.5NiO4, the CO : H2 ratio exceeds 1 at these temperatures, which is attributed to faster direct carbon dioxide conversion to SrCO3 without catalytic DRM reactivity. As no Sm2O2CO3 surface or bulk phase as a result of carbon dioxide activation was observed for any material - in contrast to La2O2CO3 - we suggest that oxy-carbonate formation plays only a minor role for DRM reactivity. Rather, we identify surface graphitic carbon as the potentially reactive intermediate. Graphitic carbon has already been shown as a crucial reaction intermediate in metal-oxide DRM catalysts and appears both for Sm1.5Sr0.5NiO4 and NiO/monoclinic Sm2O3 after reaction as crystalline structure. It is significantly more pronounced for the latter due to the higher amount of oxygen-deficient monoclinic Sm2O3 facilitating carbon dioxide activation. Despite the often reported beneficial role of earth alkaline dopants in DRM catalysis, we show that the situation is more complex. In our studies, the detrimental role of earth alkaline doping manifests itself in the exclusive formation of the sole stable carbonated species and a general destabilization of the Ni/monoclinic Sm2O3 interface by favoring Ni particle sintering.

Atomic-Scale Insights into Nickel Exsolution on LaNiO3 Catalysts via In Situ Electron Microscopy.

Using a combination of in situ bulk and surface characterization techniques, we provide atomic-scale insight into the complex surface and bulk dynamics of a LaNiO3 perovskite material during heating in vacuo. Driven by the outstanding activity LaNiO3 in the methane dry reforming reaction (DRM), attributable to the decomposition of LaNiO3 during DRM operation into a Ni//La2O3 composite, we reveal the Ni exsolution dynamics both on a local and global scale by in situ electron microscopy, in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy. To reduce the complexity and disentangle thermal from self-activation and reaction-induced effects, we embarked on a heating experiment in vacuo under comparable experimental conditions in all methods. Associated with the Ni exsolution, the remaining perovskite grains suffer a drastic shrinkage of the grain volume and compression of the structure. Ni particles mainly evolve at grain boundaries and stacking faults. Sophisticated structure analysis of the elemental composition by electron-energy loss mapping allows us to disentangle the distribution of the different structures resulting from LaNiO3 decomposition on a local scale. Important for explaining the DRM activity, our results indicate that most of the Ni moieties are oxidized and that the formation of NiO occurs preferentially at grain edges, resulting from the reaction of the exsolved Ni particles with oxygen released from the perovskite lattice during decomposition via a spillover process from the perovskite to the Ni particles. Correlating electron microscopy and X-ray diffraction data allows us to establish a sequential two-step process in the decomposition of LaNiO3 via a Ruddlesden-Popper La2NiO4 intermediate structure. Exemplified for the archetypical LaNiO3 perovskite material, our results underscore the importance of focusing on both surface and bulk characterization for a thorough understanding of the catalyst dynamics and set the stage for a generalized concept in the understanding of state-of-the art catalyst materials on an atomic level.

How the in situ monitoring of bulk crystalline phases during catalyst activation results in a better understanding of heterogeneous catalysis.

The present Highlight article shows the importance of the in situ monitoring of bulk crystalline compounds for a more thorough understanding of heterogeneous catalysts at the intersection of catalysis, materials science, crystallography and inorganic chemistry. Although catalytic action is widely regarded as a purely surface-bound phenomenon, there is increasing evidence that bulk processes can detrimentally or beneficially influence the catalytic properties of various material classes. Such bulk processes include polymorphic transformations, formation of oxygen-deficient structures, transient phases and the formation of a metal-oxide composite. The monitoring of these processes and the subsequent establishment of structure-property relationships are most effective if carried out in situ under real operation conditions. By focusing on synchrotron-based in situ X-ray diffraction as the perfect tool to follow the evolution of crystalline species, we exemplify the strength of the concept with five examples from various areas of catalytic research. As catalyst activation studies are increasingly becoming a hot topic in heterogeneous catalysis, the (self-)activation of oxide- and intermetallic compound-based materials during methanol steam and methane dry reforming is highlighted. The perovskite LaNiO3 is selected as an example to show the complex structural dynamics before and during methane dry reforming, which is only revealed upon monitoring all intermediate crystalline species in the transformation from LaNiO3 into Ni/La2O3/La2O2CO3. ZrO2-based materials form the second group, indicating the in situ decomposition of the intermetallic compound Cu51Zr14 into an epitaxially stabilized Cu/tetragonal ZrO2 composite during methanol steam reforming, the stability of a ZrO0.31C0.69 oxycarbide and the gas-phase dependence of the tetragonal-to-monoclinic ZrO2 polymorphic transformation. The latter is the key parameter to the catalytic understanding of ZrO2 and is only appreciated in full detail once it is possible to follow the individual steps of the transformation between the crystalline polymorphic structures. A selected example is devoted to how the monitoring of crystalline reactive carbon during methane dry reforming operation aids in the mechanistic understanding of a Ni/MnO catalyst. The most important aspect is the strict use of in situ monitoring of the structural changes occurring during (self-)activation to establish meaningful structure-property relationships allowing conclusions beyond isolated surface chemical aspects.

Steering the methanol steam reforming reactivity of intermetallic Cu-In compounds by redox activation: stability vs. formation of an intermetallic compound-oxide interface.

To compare the inherent methanol steam reforming properties of intermetallic compounds and a corresponding intermetallic compound-oxide interface, we selected the Cu-In system as a model to correlate the stability limits, self-activation and redox activation properties with the catalytic performance. Three distinct intermetallic Cu-In compounds - Cu7In3, Cu2In and Cu11In9 - were studied both in an untreated and redox-activated state resulting from alternating oxidation-reduction cycles. The stability of all studied intermetallic compounds during methanol steam reforming (MSR) operation is essentially independent of the initial stoichiometry and all accordingly resist substantial structural changes. The inherent activity under batch MSR conditions is highest for Cu2In, corroborating the results of a Cu2In/In2O3 sample accessed through reactive metal-support interaction. Under flow MSR operation, Cu7In3 displays considerable deactivation, while Cu2In and Cu11In9 feature stable performance at simultaneously high CO2 selectivity. The missing significant self-activation is most evident in the operando thermogravimetric experiments, where no oxidation is detected for any of the intermetallic compounds. In situ X-ray diffraction allowed us to monitor the partial decomposition and redox activation of the Cu-In intermetallic compounds into Cu0.9In0.1/In2O3 (from Cu7In3), Cu7In3/In2O3 (from Cu2In) and Cu7In3/Cu0.9In0.1/In2O3 (from Cu11In9) interfaces with superior MSR performance compared to the untreated samples. Although the catalytic profiles appear surprisingly similar, the latter interface with the highest indium content exhibits the least deactivation, which we explain by formation of stabilizing In2O3 patches under MSR conditions.

The sol-gel autocombustion as a route towards highly CO2-selective, active and long-term stable Cu/ZrO2 methanol steam reforming catalysts.

The adaption of the sol-gel autocombustion method to the Cu/ZrO2 system opens new pathways for the specific optimisation of the activity, long-term stability and CO2 selectivity of methanol steam reforming (MSR) catalysts. Calcination of the same post-combustion precursor at 400 °C, 600 °C or 800 °C allows accessing Cu/ZrO2 interfaces of metallic Cu with either amorphous, tetragonal or monoclinic ZrO2, influencing the CO2 selectivity and the MSR activity distinctly different. While the CO2 selectivity is less affected, the impact of the post-combustion calcination temperature on the Cu and ZrO2 catalyst morphology is more pronounced. A porous and largely amorphous ZrO2 structure in the sample, characteristic for sol-gel autocombustion processes, is obtained at 400 °C. This directly translates into superior activity and long-term stability in MSR compared to Cu/tetragonal ZrO2 and Cu/monoclinic ZrO2 obtained by calcination at 600 °C and 800 °C. The morphology of the latter Cu/ZrO2 catalysts consists of much larger, agglomerated and non-porous crystalline particles. Based on aberration-corrected electron microscopy, we attribute the beneficial catalytic properties of the Cu/amorphous ZrO2 material partially to the enhanced sintering resistance of copper particles provided by the porous support morphology.

Steering the Catalytic Properties of Intermetallic Compounds and Alloys in Reforming Reactions by Controlled in Situ Decomposition and Self-Activation.

Based on the increasing importance of intermetallic compounds and alloys in heterogeneous catalysis, we explore the possibilities of using selected intermetallic compounds and alloy structures and phases as catalyst precursors to prepare highly active and CO2-selective methanol steam reforming (MSR) as well as dry reforming of methane (DRM) catalyst entities by controlled in situ decomposition and self-activation. The exemplary discussed examples (Cu51Zr14, CuZn, Pd2Zr, GaPd2, Cu2In, ZnPd, and InPd) show both the advantages and pitfalls of this approach and how the concept can be generalized to encompass a wider set of intermetallic compounds and alloy structures. Despite the common feature of all systems being the more or less pronounced decomposition of the intermetallic compound surface and bulk structure and the in situ formation of much more complex catalyst entities, differences arise due to the oxidation propensity and general thermodynamic stability of the chosen intermetallic compound/alloy and their constituents. The metastability and intrinsic reactivity of the evolving oxide polymorph introduced upon decomposition and the surface and bulk reactivity of carbon, governed by the nature of the metal/intermetallic compound-oxide interfacial sites, are of equal importance. Structural and chemical rearrangements, dictating the catalytic performance of the resulting entity, are present in the form of a complete destruction of the intermetallic compound bulk structure (Cu51Zr14) and the formation of an metal/oxide (Cu51Zr14, InPd) or intermetallic compound/oxide (ZnPd, Cu2In, CuZn) interface or the intertranformation of intermetallic compounds with varying composition (Pd2Zr) before the formation of Pd/ZrO2. In this Perspective, the prerequisites to obtain a leading theme for pronounced CO2 selectivity and high activity will be reviewed. Special focus will be put on raising awareness of the intrinsic properties of the discussed catalyst systems that need to be controlled to obtain catalytically prospective materials. The use of model systems to bridge the material's gap in catalysis will also be highlighted for selected examples.

True Nature of the Transition-Metal Carbide/Liquid Interface Determines Its Reactivity.

Compound materials, such as transition-metal (TM) carbides, are anticipated to be effective electrocatalysts for the carbon dioxide reduction reaction (CO2RR) to useful chemicals. This expectation is nurtured by density functional theory (DFT) predictions of a break of key adsorption energy scaling relations that limit CO2RR at parent TMs. Here, we evaluate these prospects for hexagonal Mo2C in aqueous electrolytes in a multimethod experiment and theory approach. We find that surface oxide formation completely suppresses the CO2 activation. The oxides are stable down to potentials as low as -1.9 V versus the standard hydrogen electrode, and solely the hydrogen evolution reaction (HER) is found to be active. This generally points to the absolute imperative of recognizing the true interface establishing under operando conditions in computational screening of catalyst materials. When protected from ambient air and used in nonaqueous electrolyte, Mo2C indeed shows CO2RR activity.

Operando Fourier-transform infrared-mass spectrometry reactor cell setup for heterogeneous catalysis with glovebox transfer process to surface-chemical characterization.

We describe a new type of operando Fourier transform infrared (FTIR)-mass spectrometry setup for surface-chemical and reactivity characterization of heterogeneous catalysts. On the basis of a sophisticated all-quartz FTIR reactor cell, capable of operating between room temperature and 1000 °C in reactive gas atmospheres, the setup offers a unique opportunity to simultaneously collect and accordingly correlate FTIR surface-chemical adsorption data of the active catalyst state and FTIR gas phase data with complementary reactivity data obtained via mass spectrometry in situ. The full set of catalytic operation modes (recirculating static and flow reactor conditions) is accessible and can be complemented with a variety of temperature-programmed reaction modes or thermal desorption. Due to the unique transfer process involving a home-built portable glovebox to avoid air exposure, a variety of complementary quasi in situ characterization methods for the pre- and post-reaction catalyst states become accessible. We exemplify the capabilities for additional x-ray photoelectron spectroscopy characterization of surface-chemical states, highlighting the unique strength of combining adsorption, electronic structure, and reactivity data to gain detailed insight into the reactive state of a Cu/ZrO2 heterogeneous catalyst during methanol steam reforming operation.

Steering the Methane Dry Reforming Reactivity of Ni/La2O3 Catalysts by Controlled In Situ Decomposition of Doped La2NiO4 Precursor Structures.

The influence of A- and/or B-site doping of Ruddlesden-Popper perovskite materials on the crystal structure, stability, and dry reforming of methane (DRM) reactivity of specific A2BO4 phases (A = La, Ba; B = Cu, Ni) has been evaluated by a combination of catalytic experiments, in situ X-ray diffraction, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and aberration-corrected electron microscopy. At room temperature, B-site doping of La2NiO4 with Cu stabilizes the orthorhombic structure (Fmmm) of the perovskite, while A-site doping with Ba yields a tetragonal space group (I4/mmm). We observed the orthorhombic-to-tetragonal transformation above 170 °C for La2Ni0.9Cu0.1O4 and La2Ni0.8Cu0.2O4, slightly higher than for undoped La2NiO4. Loss of oxygen in interstitial sites of the tetragonal structure causes further structure transformations for all samples before decomposition in the temperature range of 400 °C-600 °C. Controlled in situ decomposition of the parent or A/B-site doped perovskite structures in a DRM mixture (CH4:CO2 = 1:1) in all cases yields an active phase consisting of exsolved nanocrystalline metallic Ni particles in contact with hexagonal La2O3 and a mixture of (oxy)carbonate phases (hexagonal and monoclinic La2O2CO3, BaCO3). Differences in the catalytic activity evolve because of (i) the in situ formation of Ni-Cu alloy phases (in a composition of >7:1 = Ni:Cu) for La2Ni0.9Cu0.1O4, La2Ni0.8Cu0.2O4, and La1.8Ba0.2Ni0.9Cu0.1O4, (ii) the resulting Ni particle size and amount of exsolved Ni, and (iii) the inherently different reactivity of the present (oxy)carbonate species. Based on the onset temperature of catalytic DRM activity, the latter decreases in the order of La2Ni0.9Cu0.1O4 ∼ La2Ni0.8Cu0.2O4 ≥ La1.8Ba0.2Ni0.9Cu0.1O4 > La2NiO4 > La1.8Ba0.2NiO4. Simple A-site doped La1.8Ba0.2NiO4 is essentially DRM inactive. The Ni particle size can be efficiently influenced by introducing Ba into the A site of the respective Ruddlesden-Popper structures, allowing us to control the Ni particle size between 10 nm and 30 nm both for simple B-site and A-site doped structures. Hence, it is possible to steer both the extent of the metal-oxide-(oxy)carbonate interface and its chemical composition and reactivity. Counteracting the limitation of the larger Ni particle size, the activity can, however, be improved by additional Cu-doping on the B-site, enhancing the carbon reactivity. Exemplified for the La2NiO4 based systems, we show how the delicate antagonistic balance of doping with Cu (rendering the La2NiO4 structure less stable and suppressing coking by efficiently removing surface carbon) and Ba (rendering the La2NiO4 structure more stable and forming unreactive surface or interfacial carbonates) can be used to tailor prospective DRM-active catalysts.

Spectro-electrochemical setup for in situ and operando mechanistic studies on metal oxide electrode surfaces.

This work shows a combined setup of Diffuse Reflectance FT-IR Spectroscopy (DRIFTS) and electrochemical characterization by AC and DC methods for in situ and operando investigations of surface species during CO2 electrolysis on metal oxide electrodes and their correlation with electrochemical activity. A high-temperature reaction chamber enables conducting DRIFTS and electrochemical experiments simultaneously at temperatures up to 1000 °C in both reductive and oxidative reaction atmospheres and under anodic and cathodic polarization conditions. A dedicated gas- and electrical feedthrough solution is presented, which is the key element required for recording electrochemical AC and DC characteristics using an electrochemical cell, which is simultaneously studied by DRIFTS experiments under realistic operation conditions. Selected results, obtained on a gadolinium doped ceria model solid oxide electrolysis cell upon different polarization states, demonstrate the basic functionality and capabilities of the setup and show how the simultaneous DRIFT-spectroscopic and electrochemical investigation of the surface and bulk chemistry on electrode materials leads to increased insight in the population of potential intermediates during CO2 electrolysis. With infrared spectroscopy and impedance spectroscopy as common and complementary spectroscopic methods in material science, the setup is considered to exhibit a huge potential in a wide field of fundamental and applied mechanistic research.

Increasing Complexity Approach to the Fundamental Surface and Interface Chemistry on SOFC Anode Materials.

ConspectusIn this Account, we demonstrate an increasing complexity approach to gain insight into the principal aspects of the surface and interface chemistry and catalysis of solid oxide fuel cell (SOFC) anode and electrolyte materials based on selected oxide, intermetallic, and metal-oxide systems at different levels of material complexity, as well as into the fundamental microkinetic reaction steps and intermediates at catalytically active surface and interface sites. To dismantle the complexity, we highlight our deconstructing step-by-step approach, which allows one to deduce synergistic properties of complex composite materials from the individual surface catalytic properties of the single constituents, representing the lowest complexity level: pure oxides and pure metallic materials. Upon mixing and doping the latter, directly leading to formation of intermetallic compounds/alloys in the case of metals and oxygen ion conductors/mixed ionic and electronic conductors for oxides, a second complexity level is reached. Finally, the introduction of an (inter)metall(ic)-(mixed) oxide interface leads to the third complexity level. A shell-like model featuring three levels of complexity with the unveiled surface and interface chemistry at its core evolves. As the shift to increased complexity decreases the number of different materials, the interconnections between the studied materials become more convoluted, but the resulting picture of surface chemistry becomes clearer. The materials featured in our investigations are all either already used technologically important or prospective components of SOFCs (such as yttria-stabilized zirconia, perovskites, or Ni-Cu alloys) or their basic constituents (e.g., ZrO2), or they are formed by reactions of other compounds (for instance, pyrochlores are thought to be formed at the YSZ/perovskite phase boundary). We elaborate three representative case studies based on ZrO2, Y2O3, and Y-doped ZrO2 in detail from all three complexity levels. By interconnection of results, we are able to derive common principles of the influence of surface and interface chemistry on the catalytic operation of SOFC anode materials. In situ measurements of the reactivity of water and carbon surface species on ZrO2- and Y2O3-based materials represent levels 1 and 2. The highest degree of complexity at level 3 is exemplified by combined surface science and catalytic studies of metal-oxide systems, oxidatively derived from intermetallic Cu-Zr and Pd-Zr compounds and featuring a large number of phases and interfaces. We show that only by appreciating insight into the basic building blocks of the catalyst materials at lower levels, a full understanding of the catalytic operation of the most complex materials at the highest level is possible.

Synthesis and crystal structure of ABW-type SrFe1.40V0.60O4.

Single crystals of SrFe1.40V0.60O4, strontium tetra-oxidodi[ferrate(III)/vanad-ate(III)], have been obtained as a side product in the course of sinter experiments aimed at the synthesis of double perovskites in the system SrO-Fe2O3-V2O5. The crystal structure can be characterized by layers of six-membered rings of TO4-tetra-hedra (T: FeIII, VIII) perpendicular to [100]. Stacking of the layers along [100] results in a three-dimensional framework enclosing tunnel-like cavities in which SrII cations are incorporated for charge compensation. The sequence of directedness of up (U) and down (D) pointing vertices of neighboring tetra-hedra in a single six-membered ring is UUUDDD. The topology of the tetra-hedral framework belongs to the zeolite-type ABW.

Zirconium Oxycarbide: A Highly Stable Catalyst Material for Electrochemical Energy Conversion.

Metal carbides and oxycarbides have recently gained considerable interest due to their (electro)catalytic properties that differ from those of transition metals and that have potential to outperform them as well. The stability of zirconium oxycarbide nanopowders (ZrO0.31 C0.69 ), synthesized via a hybrid solid-liquid route, is investigated in different gas atmospheres from room temperature to 800 °C by using in-situ X-ray diffraction and in-situ electrical impedance spectroscopy. To feature the properties of a structurally stable Zr oxycarbide with high oxygen content, a stoichiometry of ZrO0.31 C0.69 has been selected. ZrO0.31 C0.69 is stable in reducing gases with only minor amounts of tetragonal ZrO2 being formed at high temperatures, whereas it decomposes in CO2 and O2 gas atmosphere. From online differential electrochemical mass spectrometry measurements, the hydrogen evolution reaction (HER) onset potential is determined at -0.4 VRHE . CO2 formation is detected at potentials as positive as 1.9 VRHE as ZrO0.31 C0.69 decomposition product, and oxygen is anodically formed at 2.5 VRHE , which shows the high electrochemical stability of this material in acidic electrolyte. This peopwery makes the material suited for electrocatalytic reactions at anodic potentials, such as CO and alcohol oxidation reactions, in general.

Reactive metal-support interaction in the Cu-In2O3 system: intermetallic compound formation and its consequences for CO2-selective methanol steam reforming.

The reactive metal-support interaction in the Cu-In2O3 system and its implications on the CO2 selectivity in methanol steam reforming (MSR) have been assessed using nanosized Cu particles on a powdered cubic In2O3 support. Reduction in hydrogen at 300 °C resulted in the formation of metallic Cu particles on In2O3. This system already represents a highly CO2-selective MSR catalyst with ~93% selectivity, but only 56% methanol conversion and a maximum H2 formation rate of 1.3 µmol gCu -1 s-1. After reduction at 400 °C, the system enters an In2O3-supported intermetallic compound state with Cu2In as the majority phase. Cu2In exhibits markedly different self-activating properties at equally pronounced CO2 selectivities between 92% and 94%. A methanol conversion improvement from roughly 64% to 84% accompanied by an increase in the maximum hydrogen formation rate from 1.8 to 3.8 µmol gCu -1 s-1 has been observed from the first to the fourth consecutive runs. The presented results directly show the prospective properties of a new class of Cu-based intermetallic materials, beneficially combining the MSR properties of the catalyst's constituents Cu and In2O3. In essence, the results also open up the pathway to in-depth development of potentially CO2-selective bulk intermetallic Cu-In compounds with well-defined stoichiometry in MSR.