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The Meran-Mauls nappe stack is part of the Austroalpine unit in South Tyrol (Italy). There it holds a special position directly in front of the Southalpine Dolomites indenter and west of the Tauern Window. It is situated in the hanging wall of the Southalpine unit, above a NW dipping segment of the Periadriatic fault system, namely the Meran-Mauls fault. Also all other sides are defined by Oligocene-Miocene strike-slip and normal faults. Based on recent mapping the Meran-Mauls nappe stack consists of three nappes separated by NW to NNW dipping shear zones. The lowermost nappe in the southwest is represented by the Schenna (Scena) unit. It is overlain along the Masul shear zone by a nappe consisting of the Hirzer (Punta Cervina) unit and the Pens (Pennes) unit including Triassic (meta)sediments. Separated by the Fartleis fault the St. Leonhard (San Leonardo) unit forms the uppermost nappe. The aim of this study is to describe the individual units and the separating structural elements more properly, based on new structural, petrological, geothermobarometric and geochronological data and to compare these units to other Austroalpine elements in the vicinity. Sillimanite-bearing paragneiss, minor amphibolite and quartzite as well as a distinct marble layer close to its base characterise the Schenna unit. Further, it contains pegmatite dikes, presumably Permian in age. Amphibolite-facies P-T conditions of c. 0.55 ± 0.15 GPa and 600 ± 100°C are thus correlated with a Permian metamorphic imprint. The Masul shear zone mostly consists of mylonitic paragneiss of the Hirzer unit. It is pre-Alpine in age and probably formed during the Jurassic. For the paragneiss of the Hirzer unit upper greenschist- to amphibolite-facies metamorphic conditions of 0.4-0.50 ± 0.15 GPa and 550 ± 70°C are attributed to the Variscan tectonometamorphic imprint. The whole Pens unit represents a shear zone. Due to the occurrence of Permotriassic (meta)-sediments within this shear zone, it is an Alpine structure, as well as the bordering Fartleis fault. Rb/Sr biotite ages yield sometimes partly reset pre-Alpine age values in the whole Meran-Mauls nappe stack, indicating a pervasive anchizonal to lowermost greenschist-facies metamorphic overprint during the Eoalpine tectonometamorphic event. Tectonostratigraphically the Meran-Mauls nappe stack can be attributed to the Drauzug-Gurktal nappe system. The latter forms the uppermost structural element of the Austroalpine nappe stack and thus only shows a weak Eoalpine metamorphic overprint. With respect to its special lithologic composition the Schenna unit can be correlated with the Tonale unit in the southwest and the Strieden-Komplex in the east.

The Ötztal-Nappe in the central Eastern Alps represents a classical area of polyphase deformation and metamorphism. The pre-Mesozoic basement (Ötztal-Stubai Complex; OSC) comprises metasediments (paragneiss and mica schist), metaigneous rocks and metabasites that experienced a polymetamorphic overprint during Ordovician, Variscan (Devonian to Carboniferous) and Eo-Alpine (Early/Late Cretaceous) events. In the Stubai Alps, basement rocks are unconformably overlain by a monometamorphic Permo-Triassic cover sequence (i.e. “Brenner-Mesozoic”), which truncates pre-Mesozoic structures and allows discriminating pre-Alpine and (Eo-)Alpine structures.Ordovician metagranites (analysed using LA-ICP-MS U-Pb dating of zircon), deformed together with their metasedimentary host rock, highlight the large-scale structure of the OSC. During the Variscan event, metabasitic rocks of the central OSC underwent eclogite-facies metamorphism followed by an amphibolite-facies overprint. Two pre-Alpine fold generations can be distinguished: i) NE-dipping fold axes of isoclinal folds overprinted by ii) subhorizontal NW-SE trending fold axes that are associated with a pervasive axial plane foliation. Shearbands dissecting the foliation indicate a top-NE directed shear sense, which probably correlates with post-Variscan exhumation. Locally, the shearbands show a SE-directed overprint, which is attributed to Late Cretaceous extension in the course of the Eo-Alpine event.(Eo-)Alpine metamorphism of the Ötztal-Nappe, represented by a southward increasing gradient from greenschist-facies conditions in the northwest to epidote-amphibolite-facies conditions in the southeast, led to a differential structural overprint. Ar-Ar white mica ages from the Stubai Alps yielding Middle to Upper Pennsylvanian ages (post-Variscan cooling) and “mixed” Variscan-to-Alpine ages reflect the metamorphic gradient. Late Cretaceous ages from Rb-Sr analyses on biotite and (U-Th)/He) zircon thermochronology provide time constraints on large detachment faults that created several tectonic klippen of Mesozoic rocks in the study area. These detachments formed in a general SE-directed extensional regime, which is widely reported from Upper Austroalpine units.

The Adriatic Indenter is subdivided into a western and an eastern domain termed Canavese-Insubric Indenter and Dolomites Indenter, respectively, and offset for ~75 km from late Oligocene onwards by the NNE‐SSW‐trending sinistral-transpressive Giudicarie fault system (GFS). The N(NW)-directed movement of the Dolomites Indenter (DI) modifies the early Cenozoic nappe structure of the Alpine orogen as the accommodated shortening changes substantially, depending on the oblique shape of the indenter and its counter-clockwise rotation. The Austroalpine basement units northwest of the GFS experienced open folding of the Cretaceous nappe stack and preserved Cretaceous metamorphic ages. In contrast, the previously deep-seated Neoalpine metamorphic Subpenninic and Penninic units of the Tauern Window in front of the DI’s tip are exhumed and the Austroalpine units adjacent to the DI are brought into a subvertical or even overturned position. The combination of several thermochronological methods and structural field work allows for constraining time on this tectonic evolution: The Austroalpine units directly adjacent to the DI belong to the uppermost nappe system of the Eoalpine orogeny (Drauzug-Gurktal Nappe System) and experienced an anchizonal to lowermost greenschist-facies metamorphic overprint during the Alpine orogeny resulting in an only partial reset of Variscan Rb/Sr Biotite ages (Pomella et al., 2022). Fission track data from the western Tauern Window and the Austroalpine units adjacent to the north-western corner of the DI, indicate cooling below 180-200°C (Zircon Fission track data) in the Early Miocene and below the 100-120°C (Apatite Fission track data) in the Late Miocene (Klotz et al., 2019). (U‐Th)/He on Apatite data, derived from a horizontal section of the Brenner Base Tunnel and reaching from the DI into the Austroalpine nappe stack, indicate continuous differential uplifting of the northern block along the, in this area, approximately E‑W striking Periadriatic fault system until the Pliocene (Klotz et al., 2019). Earthquake focal solutions and satellite-based geodetic studies show, that indentation is ongoing today. The significant present-day seismotectonic activity concentrates in the Friuli area in the southeast, whereas there is currently no significant seismicity along the western and northern boundaries of the DI or in the northerly adjacent Austroalpine basement and the Tauern Window. Increased seismic activity can only be detected north of the Tauern Window, along, and north of the Inn Valley (Reiter et al., 2018). Based on field evidence and the thermochronological record, the recent seismic distribution indicates an important change in style and localisation of deformation compared to what is documented from the past. Klotz, T., Pomella, H., Reiser, M., Fügenschuh, B., Zattin, M., 2019. Differential uplift on the boundary between the Eastern and the Southern European Alps: Thermochronologic constraints from the Brenner Base Tunnel. Terra Nova 31, 281-294. Pomella, H., Costantini, D., Aichholzer, P., Reiser, M., Schuster, R., Tropper, P., 2022. Petrological and geochronological investigations on the individual nappes of the Meran-Mauls nappe stack (Austroalpine unit/South Tyrol, Italy). Austrian Journal of Earth Sciences 115, 15-40. Reiter, F., Freudenthaler, C., Hausmann, H., Ortner, H., Lenhardt, W., Brandner, R., 2018. Active seismotectonic deformation in front of the Dolomites indenter, Eastern Alps. Tectonics 37, 4625-4654.

This contribution reports LA-ICP-MS zircon ages and Rb-Sr biotite ages from the Troiseck-Floning Nappe, forming the northeasternmost extension of the Silvretta-Seckau Nappe System in the Eastern Alps. The Troiseck-Floning Nappe comprises a basement formed by the Troiseck Complex and a Permo-Triassic cover sequence. The basement consists of paragneiss with intercalations of micaschist, amphibolite and different types of orthogneiss, which was affected by a Variscan (Late Devonian) amphibolite facies metamorphic overprint. The cover sequence includes Permian clastic metasediments and metavolcanics, as well as Triassic quartzite, rauhwacke, calcitic marble and dolomite. During the Eoalpine (Cretaceous) tectonothermal event the nappe experienced deformation at lower greenschist facies conditions. Detrital zircon grains from paragneiss are in the range of 530-590 Ma, indicating an Ediacarian to earliest Cambrian source and a Cambrian to Ordovizian deposition age of the protolith. Late Cambrian to Ordovician crystallization ages from leucogranitic intrusions represent the earliest magmatic event of the Troiseck Complex. The amphibolite bodies derived from basalt with a calc-alkaline to island arc tholeiitic signature. Leucocratic orthogneiss with K-feldspar porphyroclasts and a calc-alkaline granitic composition plots in the field of volcanic arc granite. The youngest zircon grains indicate a Late Devonian crystallization. Two pegmatite gneisses with a calc-alkaline composition are early Mississippian in age. Mylonitic orthogneiss with a pronounced stretching lineation appears as irregularly shaped layers. It is leucocratic, very fine grained and contains scattered feldspar porphyroclasts with a round shape and a diameter of about 1 mm. Its chemical composition is granitic/rhyolitic with an alkali-calcic signature. In classification diagrams it plots in the field of syn-collision granite. Zircon ages of about 270 Ma indicate a Permian crystallization. Similar rocks interpreted as Permian rhyolitic metavolcanics appear in the cover sequence. They share a similar chemical composition and crystallization age of 270 Ma. Associated intermediate metavolcanics developed from calc-alkaline basaltic andesite. According to Rb-Sr biotite ages cooling of the Troiseck-Floning Nappe below c. 300°C occurred at about 85 Ma in the west and 75 Ma in the east. In summary, the Troiseck Complex developed from Cambrian to Ordovizian clastic metasediments and granitic and basaltic magmatic rocks emplaced in the same time range. During the Late Devonian, it was affected by the Variscan collisional event, causing deformation at amphibolite facies conditions and intrusion of calc-alkaline granites. In early Mississippian time pegmatite dikes intruded, maybe induced by decompression and exhumation. The deposition of clastic sediments and (sub)volcanic rocks (rhyolite and basaltic andesite) constrains a surface position of the Troiseck Complex during the Permian. Based on regional considerations an extensional environment is assumed. In Triassic times carbonate platform sediments were deposited. During the Eo-Alpine collision in the Cretaceous the unit was part of the tectonic lower plate and subducted to shallow crustal levels, indicated by a lower greenschist facies metamorphic overprint. The Troiseck-Floning Nappe was formed and exhumed since about 85 Ma. Rb-Sr as well as apatite fission track data from the literature indicate tilting with more pronounced exhumation and erosion in the eastern part during Miocene lateral extrusion of the Eastern Alps.

Lithium ist ein Metall, das in der heutigen Gesellschaft unverzichtbar geworden ist und dessen Bedarf weiter steigt. Dadurch konnten in Zukunft auch kleinere Lagerstatten, wie die Spodumen-Pegmatite im Ostalpinen Kristallin, eine wirtschaftliche Bedeutung erlangen. Diese Pegmatite entstanden im Perm wahrend eines temperaturbetonten Metamorphoseereignisses. Detaillierte mineralogische und chemische Analysen sprechen dafur, dass die Schmelzen der Spodumen-Pegmatite durch Anatexis von Al-reichen, Staurolith-fuhrenden Metapeliten bei Metamorphosebedingungen von ca. 675 °C und 6,45 kbar gebildet wurden. Diese Schmelzen waren primar an Li angereichert, und durch fraktionierte Kristallisation von einfachen Graniten und Leukograniten erhohte sich der Li-Gehalt auf uber 7000 ppm, sodass letztendlich Spodumen kristallisieren konnte. Dieses Genesemodell kommt ohne grose, mit den Pegmatiten genetisch verbundene Granitkorper aus, welche im Ostalpinen Kristallin fehlen. Es liegt nahe, dass bei der Prospektion auf Spodumen-Pegmatite auch metamorphe Einheiten mit teilweise aufgeschmolzenen Glimmerschiefern und Gneisen beachtet werden sollten.

The functionality of porphyrin/oxide interfaces depends on both the structure of the organic layer and the metalation of the porphyrin units. While the structure of the porphyrin film is known to b...

Low‐temperature synthesis in ionic liquids (ILs) offers an efficient route for the preparation of metal oxide nanomaterials with tailor‐made properties in a water‐free environment. In this work, we investigated the role of 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C4C1Pyr][NTf2] in the synthesis of cobalt oxide nanoparticles from the molecular precursor Co2(CO)8 with ozone. We performed a model study in ultra‐clean, ultrahigh vacuum (UHV) conditions by infrared reflection absorption spectroscopy (IRAS) using Au(111) as a substrate. Exposure of the pure precursor to ozone at low temperatures results in the oxidation of the first layers, leading to the formation of a disordered CoxOy passivation layer. Similar protection to ozone is also achieved by deposition of an IL layer onto a precursor film prior to ozone exposure. With increasing temperature, the IL gets permeable for ozone and a cobalt oxide film forms at the IL/precursor interface. We show that the interaction with the IL mediates the oxidation and leads to a more densely packed CoxOy film compared to a direct oxidation of the precursor., Low‐temperature & Co.: We investigate the ozone‐mediated preparation of CoxOy in an IL under UHV to study interactions between the reactants by varying deposition order and temperature of the system. We show that the IL and initially formed CoxOy layer protect the precursor against oxidation. This effect is lost at elevated temperatures

At the northwestern margin of the Gurktal Alps (Eastern Alps), Eoalpine (Cretaceous) thrusting of carbonaceous material (CM) bearing metasediments formed a very low- to low-grade metamorphic nappe stack above higher-grade metamorphic basement nappes. Sedimentary burial as well as progressive metamorphism transformed the enclosed CM to anthracite, metaanthracite and semigraphite. In a kinematically well-constrained section at the northwestern frontal margin of the nappe stack, this transformation has been investigated by vitrinite reflectance measurements and Raman spectroscopy of carbonaceous materials (RSCM). Automated, interactive fitting of Raman spectra estimates the metamorphic peak temperatures in a complete section through the upper part of the Upper Austroalpine unit. A RSCM trend indicates a temperature profile of ca. 250–600 °C. The top part of the gradient is reconstructed by one-dimensional thermal modeling. The certainty of ca. ± 25 °C at a confidence level of 0.9 resembles the data variability within a sample location. Due to the large calibration range, the method is able to reconstruct a thermal crustal profile in space and time. The study highlights the versatility of RSCM, which characterizes almost 250 Ma of a complex and polyphase tectonic history. RSCM data characterize the Variscan metamorphic grade in nappes now imbricated in the Eoalpine nappe stack. They additionally constrain a numerical model which emphasizes the significance of an increased thermal gradient in a continental margin towards the western Neotethyan ocean during Permo-Triassic lithospheric extension. It finally characterizes the Eoalpine metamorphic gradient during nappe stacking and a significant metamorphic jump related to exhumation and normal faulting.

This work describes the Freyenstein Fault System, which extends over 45 km in the southeastern part of the Bohemian Massif (Lower Austria). It represents a ductile shear zone overprinted by a brittle fault located at the eastern edge of the South Bohemian Batholith towards the Moldanubian nappes. It affects Weinsberg- and a more “fine-grained” granite, interlayered aplitic granite and pegmatite dikes as well as paragneiss of the Ostrong Nappe System. The ductile shear zone is represented by approximately 500 m thick greenschist-facies mylonite dipping about 60° to the southeast. Shear-sense criteria like clast geometries, SCC`-type shear band fabrics as well as abundant microstructures show top to the south/ southsouthwest normal shearing with a dextral strike-slip component. Mineral assemblages in mylonitized granitoid consist of pre- to syntectonic muscovite- and biotite-porphyroclasts as well as dynamically recrystallized potassium feldspar, plagioclase and quartz. Dynamic recrystallization of potassium feldspar and the stability of biotite indicate upper green-schist-facies metamorphic conditions during the early phase of deformation. Fluid infiltration at lower greenschist-facies conditions led to local sericitization of feldspar and synmylonitic chloritisation of biotite during a later stage of ductile deformation. Finally, a brittle overprint by a north-south trending, subvertical, sinistral strike-slip fault that shows a normal component is observed. Ductile normal shearing along the Freyenstein Shear Zone is interpreted to have occurred between 320 Ma and c. 300 Ma. This time interval is indicated by literature data on the emplacement of the hostrock and cooling below c. 300°C inferred from two Rb-Sr biotite ages measured on undeformed granites close to the shear zone yielding 309.6 ± 3 Ma and 290.9 ± 2.9 Ma, respectively. Brittle sinistral strike-slip faulting at less than 300°C presumably took place not earlier than 300 Ma. Early ductile shearing along the Freyenstein Fault System may be genetically, but not kinematically linked to the Strudengau Shear Zone, as both acted in an extensional regime during late Variscan orogenic collapse. A relation to other major northeast-southwest trending faults of this part of the Bohemian Massif (e.g. the Vitis-Pribyslav Fault System) is indicated for the phase of brittle sinistral movement.

Review of scientific instruments 93(6), 065111 (2022). doi:10.1063/5.0087864, Characterizing electrode surface structures under operando conditions is essential for fully understanding structure-activity relationships in electrocatalysis. Here, we combine in a single experiment, high-energy surface x-ray diffraction as characterizing technique with a rotating disk electrode to provide steady state kinetics under electrocatalytic conditions. Using Pt(111) and Pt(100) model electrodes, we show that full crystal truncation measurements are readily possible up to rotation rates of 1200 RPM. Furthermore, we discuss possibilities for both potentiostatic as well as potentiodynamic measurements, demonstrating the versatility of this technique. These different modes of operation, combined with the relatively simple experimental setup, make the combined rotating disk electrode - surface x-ray diffraction experiment a powerful technique for studying surface structures under operando electrocatalytic conditions., Published by American Institute of Physics, [S.l.]

The interaction of water with metal oxides controls their activity and stability in heterogeneous catalysis and electrocatalysis. In this work, we combine density functional theory calculations and infrared reflection absorption spectroscopy (IRAS) to identify the structural motifs formed upon interaction of water with an atomically defined Co3O4(111) surface. Three principal structures are observed: (i) strongly bound isolated OD, (ii) extended hydrogen-bonded OD/D2O structures, and (iii) a third structure which has not been reported to our knowledge. In this structure, surface Co2+ ions bind to three D2O molecules to form an octahedrally coordinated Co2+ with a "half hydration shell". We propose that this hydration structure represents an important intermediate in reorganization and dissolution on oxide surfaces which expose highly unsaturated surface cations.

Physical chemistry, chemical physics 23(2), 1371 - 1380 (2021). doi:10.1039/D0CP05606E, Efficient hydrogen release from liquid organic hydrogen carriers (LOHCs) requires a high level of control over the catalytic properties of supported noble metal nanoparticles. Here, the formation of carbon-containing phases under operation conditions has a direct influence on the activity and selectivity of the catalyst. We studied the formation and stability of carbide phases using well-defined Pd/α-Al$_2$O$_3$(0001) model catalysts during dehydrogenation of a model LOHC, methylcyclohexane, in a flow reactor by in situ high-energy grazing incidence X-ray diffraction. The phase composition of supported Pd nanoparticles was investigated as a function of particle size and reaction conditions. Under operating conditions, we detected the formation of a Pd$_x$C phase followed by its conversion to Pd$_6$C. The dynamic stability of the Pd$_6$C phase results from the balance between uptake and release of carbon by the supported Pd nanoparticles in combination with the thermodynamically favorable growth of carbon deposits in the form of graphene. For small Pd nanoparticles (6 nm), the Pd$_6$C phase is dynamically stable under low flow rate of reactants. At the high reactant flow, the Pd$_6$C phase decomposes shortly after its formation due to the growth of graphene. Structural analysis of larger Pd nanoparticles (15 nm) reveals the formation and simultaneous presence of two types of carbides, Pd$_x$C and Pd$_6$C. Formation and decomposition of Pd$_6$C proceeds via a Pd$_x$C phase. After an incubation period, growth of graphene triggers the decomposition of carbides. The process is accompanied by segregation of carbon from the bulk of the nanoparticles to the graphene phase. Notably, nucleation of graphene is more favorable on bigger Pd nanoparticles. Our studies demonstrate that metastability of palladium carbides associated with dynamic formation and decomposition of the Pd$_6$C and Pd$_x$C phases is an intrinsic phenomenon in LOHC dehydrogenation on Pd-based catalysts and strongly depends on particle size and reaction conditions., Published by RSC Publ., Cambridge

Secondary minerals occur within the tholeiitic basalts of Salsette Island in the greater Mumbai region, as well as in other localities in the Deccan Volcanic Province (DVP). However, the secondary minerals of Salsette Island show remarkable differences with respect to their mineral speciation and precipitation sequence, which are both due to their unique geological environment. The greater Mumbai region is built up by the Salsette subgroup, which represents the youngest sequence of the DVP. It formed subsequently to the main phase of DVP activity in Danian time (62.5 to 61.5 Ma), in the course of the India–Laxmi Ridge–Seychelles breakup. The main part of the Salsette subgroup consists of tholeiitic basaltic flows with pillows, pillow breccia, and hyaloclastite, which formed in contact with brackish and fresh water in a lagoonal environment. In some places, intertrappeans are represented by fossiliferous shallow water sediments. On the top, trachytic and rhyolitic subaqueous volcaniclastics occur, and some dioritic bodies have intruded nearby. Due to differing fluid rock interactions, several distinctly different secondary minerals developed in the void spaces of the hyaloclastite breccia of the interpillow matrix and in the pillow cavities. The highly permeable hyaloclastite breccia formed an open system, where pronounced precipitation occurred in the early phase and at higher temperatures. In contrast, the pillow cavities were a temporally closed system and contained, for example, more low-temperature zeolites. The genesis of the secondary minerals can be summarized as follows: During initial cooling of the volcanic rocks at about 62 Ma, the first mineralization sequence developed with chlorite, laumontite I, quartz, and calcite I. Ongoing magmatic activity caused reheating and the main phase of precipitation at prehnite–pumpellyite facies conditions. During generally decreasing temperatures, in the range of 270–180 °C, babingtonite, laumontite II, prehnite, julgoldite, yugawaralite, calcite II, ilvaite, pumpellyite, and gryolite developed. The fluid contained SiO2 + Al2O3 + FeO + MgO + CaO, and minor MnO and Na2O, and was predominately mineralized by the decomposition of basaltic glass. Further temperature decreases caused zeolite facies conditions and precipitation of okenite I, scolecite, heulandite, stilbite, and finally chabazite I, in the temperature range of 180 °C to less than 100 °C. As FeO, MgO, and MnO were then absent, an interaction of the fluid with plagioclase is indicated. According to Rb-Sr and K-Ar ages on apophyllite-K, a third phase of precipitation with apophyllite-K, okenite II, and chabazite II occurred in the late Eocene to early Oligocene (30–40 Ma). The new hydrothermal fluid additionally contained K2O, and temperatures of 50–100 °C can be expected.

The Mt. Papuk heteroadcumulate pyroxene-amphibole gabbronorites, which outcrops at the southern margin of the Tisza Mega-Unit is suggested to stem from the deep oceanic crust formed by the in situ crystallization in a supposed magma chamber. Amphibole oikocrystals are found to define a poikilitic texture of analysed rocks. A common enclosure in amphibole is the cumulus orthopyroxene, and rarely, the clinopyroxene and/or plagioclase and spinel. The chemical composition of related minerals and their crystallization sequence suggest the sub-solidus crystallization of gabbronorite in an open system at high temperatures and medium pressures. Parental magmas originated from the moderately depleted mantle source, which was metasomatized prior to melting. Early mineral fractionation gave rise to the assemblage consisted of spinel, pyroxene, plagioclase and intecumulus amphibole. The rocks’ bulk chemistry, mineral crystallization sequence, pyroxene geochemistry and myriad of high-Ca plagioclase, which coexists with igneous Ca-amphibole are all in favour of the strong subduction influence typical for mafic intrusion formed above mantle wedge in the root of an island arc at depths of 10 to 21 km. Herein presented geochemical and isotopic data (40Ar-39Ar: 487.1 ± 4.3 Ma and Sm-Nd: 505 Ma) to go along with existence of an intra-oceanic arc related to geodynamic events that took place in the Prototethyan oceanic realm s.l. during middle Cambrian to earliest Ordovician. These events were likely correlated with the subduction of the Quaidam(?) back-arc ocean, or alternatively, with the subduction and closure of Prototethyan branches located between microcontinental fragments of Asia. Initially, the closure of back- arc oceans led to crust fragmentation and, then, addition of non-metamorphosed mafites into the obducted sequence further from the active continental margins of Gondwana and Laurassia at the time of the formation of Pangea in the late Palaeozoic.

The Dinaridic segment of Neotethys was affected by a widespread shortening and related subduction-accretion-obduction processes that commenced in the middle Jurassic. In the Dinarides, the Krivaja-Konjuh Ophiolite Complex (KKOC) stands as the largest ophiolite complex with a well-exposed metamorphic sole which is the key to understanding the dynamics of intraoceanic subduction initiation in this part of Neotethys. In this contribution we present Sm-Nd geochronology on a granulite facies amphibolite from the KKOC, as well as a detailed petrological description. A five-point isochrone age calculated from clinopyroxene, plagioclase, garnet, amphibole and whole rock is 162 ± 14 Ma (MSWD = 6.2), whereas garnet and whole rock yield 160 ± 7 Ma. Ages calculated from all data points except clinopyroxene are 162 ± 5 Ma (MSWD = 1.09). Petrographic investigations suggest that these ages date granulite facies metamorphic conditions (i.e. peak metamorphism of Grt-Cpx amphibolite) rather than post-peak exhumation or obduction processes. Phase textural relationships are in line with previous research, which indicated a peak metamorphism equilibration pressure and temperature of ~1 GPa and ~800 °C, respectively. Granulite facies conditions are elucidated for an igneous precursor, which underwent a multi-stage metamorphism that gave rise to recrystallization of igneous clinopyroxene and plagioclase, epitaxial growth of amphibole, and garnet blastosis. Taking into account the age of gabbronorite from the youngest segment of the KKOC oceanic crust (Taorcian to Bathonian) and ages of radiolarian assemblages from the KKOC mélange (Bajocian to Bathonian), it may be inferred that within ~25 Ma the Dinaridic segment of Neotethys evolved rapidly from active ridge spreading through a stage of intraoceanic subduction and arc magmatism toward sub-ophioliteexhumation and further obduction along the Adria passive margin at the end of the Jurassic era.

The Tisza and Dacia mega-units constitute a central part of the Alps-Carpathians-Dinarides orogenic system. Polyphase medium-grade metamorphism observed in mineral assemblages from the crystalline basement is often correlated with Variscan and pre-Variscan events. However, a mid-Cretaceous Sm–Nd garnet age (103.6 ± 1.8 Ma) from the Apuseni Mountains is at odds with this interpretation. Electron-microprobe U-Th–Pb dating of monazite in samples from the Apuseni Mountains, the Rodna Mountains, as well as the Simleu Silvaniei, Ticau and Preluca inselbergs revealed a complex pattern of Alpine and pre-Alpine age clusters. Pre-Variscan and Variscan ages were obtained from the core of zoned monazite grains and from samples that apparently escaped Alpine overprinting. Relic monazite in the latter is often replaced by rhabdophane and/or surrounded by allanite coronas. Permian to Early Triassic monazite ages correlate with the intrusion of granitic melts and pegmatites. Early Cretaceous ages from rims of chemically zoned grains and from monazite inclusions in garnet, biotite and staurolite represent newly formed metamorphic grains that crystallized on the prograde path during Alpine metamorphism. Petrographic observations of prograde allanite breakdown reactions, Sm–Nd garnet analyses and thermobaric estimates (500–550 °C/5–8 kbar) from parts of the Tisza and Dacia mega-units constrain medium-grade conditions during Early Cretaceous times. Exclusively mid-Cretaceous monazite ages from the inselbergs and the Rebra-Unit of the Rodna Mountains, allow extending the Alpine prograde overprint across the Transylvanian basin. Together with other studies from the basement of the Pannonian basin, this implies that the Dacia Mega-Unit and parts of the Tisza Mega-Unit experienced a medium-grade metamorphic overprint and synkinematic garnet-growth during late Early Cretaceous times. The Alpine prograde medium-grade overprint is pronounced in the contact zone between the Tisza and Dacia mega-units and forms a continuous belt with the Cretaceous metamorphic imprint in the Eastern Alps, when back-rotated to its original position during the Cretaceous.

Electronic metal–support interactions play a key role in the design of heterogeneous catalysts, as they provide a tool for tuning catalytic properties and enhancing catalyst stability. In this work...

Electrocatalysis is at the heart of our future transition to a renewable energy system. Most energy storage and conversion technologies for renewables rely on electrocatalytic processes and, with increasing availability of cheap electrical energy from renewables, chemical production will witness electrification in the near future1-3. However, our fundamental understanding of electrocatalysis lags behind the field of classical heterogeneous catalysis that has been the dominating chemical technology for a long time. Here, we describe a new strategy to advance fundamental studies on electrocatalytic materials. We propose to 'electrify' complex oxide-based model catalysts made by surface science methods to explore electrocatalytic reactions in liquid electrolytes. We demonstrate the feasibility of this concept by transferring an atomically defined platinum/cobalt oxide model catalyst into the electrochemical environment while preserving its atomic surface structure. Using this approach, we explore particle size effects and identify hitherto unknown metal-support interactions that stabilize oxidized platinum at the nanoparticle interface. The metal-support interactions open a new synergistic reaction pathway that involves both metallic and oxidized platinum. Our results illustrate the potential of the concept, which makes available a systematic approach to build atomically defined model electrodes for fundamental electrocatalytic studies.

We have studied particle size effects on atomically-defined model catalysts both in ultrahigh vacuum (UHV) and under electrochemical (EC) conditions in liquid electrolytes. The model catalysts were prepared in UHV by physical vapour deposition (PVD) of Pt onto an ordered Co3O4(111) film on Ir(100), yielding nanoparticles (NPs) with an average size from 10 to 500 atoms per particle (0.8 to 3 nm). The model systems were characterized in UHV using surface science methods including scanning tunnelling microscopy (STM), before transferring them out of the UHV and into the electrolyte without contact to ambient conditions. By X-ray photoelectron spectroscopy (XPS) we show that the model surfaces are stable in the EC environment under the applied conditions (0.1 to 1 M phosphate buffer, pH 10, 0.33 to 1.03 VRHE). As a reference, we study Pt(111) under identical conditions. In UHV, we also investigated the adsorption of CO using infrared reflection absorption spectroscopy (IRRAS). Under EC conditions, we performed equivalent experiments using EC infrared reflection absorption spectroscopy (EC-IRRAS) in combination with cyclic voltammetry (CV). Characteristic differences were observed between the IR spectra under EC conditions and in UHV. Besides the red-shift induced by the interfacial electric field (Stark effect), the EC IR bands of CO on Pt(111) show a larger width (by a factor of 2) as a result of local variations in the CO environment and coupling to the electrolyte. The CO IR bands of the Pt NPs are even broader (by a factor of 5), which is attributed to local variations of the interfacial electric field at the NP surface. Further pronounced differences are observed between the spectra taken in UHV and in the electrolyte regarding the site occupation and its dependence on particle size. In UHV, adsorption at on-top sites is preferred on Pt(111) at low coverage and similar adsorption ratios of on-top and bridge-bonded CO are formed at saturation coverage. In sharp contrast, on-top adsorption of CO on Pt(111) is partially suppressed under EC conditions. This effect is attributed to the competitive adsorption of anions from the electrolyte and leads to a clear preference for bridge sites at higher potentials (>0.5 VRHE). For the Pt NPs, the situation is different and an increasing fraction of on-top CO is observed with decreasing particle size, both under EC conditions and in UHV. For the smallest particles (10–20 atoms) we do not detect any bridge-bonded CO. This change in site preference as a function of particle size is attributed to stronger on-top adsorption on low-coordinated Pt atoms of small Pt NPs. The effect leads to a clear preference for on-top adsorption in the electrolyte even at low CO coverage and over the full potential range studied.

The Variscan European Belt is a complex orogen with its southern margin partly obscured by Alpine tectonics and metamorphism. We present a study of one of the units, the Seckau Complex, that constitute the southern part of the Variscan European Belt in the Eastern Alps in order to clarify its origin, age and lithostratigraphy. The magmatic and geochronological evolution of this Complex in the northwestern part of the Seckau Nappe (as part of the Austroalpine Silvretta-Seckau Nappe System) was investigated by zircon U Pb dating of paragneisses and metagranitoids coupled with petrological and geochemical data. This reveals the distinction of three newly defined lithostratigraphic/lithodemic sub-units: (1) Glaneck Metamorphic Suite, (2) Hochreichart Plutonic Suite and (3) Hintertal Plutonic Suite. The Glaneck Metamorphic Suite is mainly composed of fine-grained paragneisses that yield U Pb zircon ages in the range between 2.7 Ga and 2.0 Ga, as well as concordia ages from 572 ± 7 Ma to 559 ± 11 Ma. All of these ages are interpreted as detrital zircon ages originating from an igneous source. The paragneisses are the host rock for the large volumes of metagranitoids of the Hochreichart Plutonic Suite and the Hintertal Plutonic Suite. The Hochreichart Plutonic Suite comprises highly fractionated melts with mainly S-type characteristics and late Cambrian to Early Ordovician U Pb zircon ages (508 ± 9 Ma to 486 ± 9 Ma), interpreted as magmatic protolith ages. The Hintertal Plutonic Suite is composed of metagranitoids with Late Devonian to early Carboniferous (365 ± 11 Ma and 331 ± 10 Ma) protolith ages, that intruded during an early phase of the Variscan tectonometamorphic event. The metagranitoids of the Hintertal Plutonic Suites define a magmatic fractionation trend, seen in variable Rb/Sr ratios. On this base they can be further subdivided into (a) the Griessstein Pluton characterized by S-type metagranitoids and (b) the Pletzen Pluton distinguished by intermediate to acidic metagranitoids with I-type affinity. The detrital zircon age spectra suggest a Neoproterozoic ancestry of the Glaneck Metamorphic Suite, which was located west of the Arabian Nubian Shield, probably next to the Trans-Saharan Belt. The early Paleozoic evolution of the recent Seckau Complex shows similarities to basement units of the Southalpine Unit, parts of the Austroalpine Unit and the Tatric and Veporic units of the Central Western Carpathians.

The changing shape of indenting crustal blocks during northward motion of the Adriatic microplate induced migration of Miocene doming and orogen-parallel extension of orogenic crust in the Tauern Window. New structural and kinematic data indicate that initial shortening of the Penninic nappe pile in the Tauern Window by upright folding and strike-slip faulting was transitional to coeval north-south shortening and east-west extension; the latter was accommodated by normal faulting at the eastern and western margins of the window. Retrodeforming these post-nappe structures in map view yields a map-view reconstruction of the orogenic crust back to 30 Ma, including the onset of pronounced indentation at ~21 Ma. This model supports the notion that indentation involved approximately equal amounts of north-south shortening and orogen-parallel stretching and extrusion toward the Pannonian Basin, as measured from the indenter tip to the European foreland in the north and Austroalpine units in the east. Comparison of areal denudation of the orogenic crust before and after indentation indicate that erosion associated with upright folding was the primary agent of denudation, whereas extensional unroofing and limited erosion along normal faults at the eastern and western ends of the Tauern Window accounted for only about a third of the total denudation.

Basement rocks from the Biharia Nappe System in the Apuseni Mountains comprise several dolomite and calcite marble sequences or lenses which experienced deformation and metamorphic overprint during the Alpine orogeny. New Sr, O and C-isotope data in combination with considerations from the lithological sequences indicate Middle to Late Triassic deposition of calcite marbles from the Vulturese-Belioara Series (Biharia Nappe s.str.). Ductile deformation and large-scale folding of the siliciclastic and carbonatic lithologies is attributed to NW-directed nappe stacking during late Early Cretaceous times (D2). The studied marble sequences experienced a metamorphic overprint under lower greenschist- facies conditions (316-370 °C based on calcite - dolomite geothermometry) during this tectonic event. Other marble sequences from the Biharia Nappe System (i.e. Vidolm and Baia de Arieș nappes) show similarities in the stratigraphic sequence and their isotope signature, together with a comparable structural position close to nappe contact. However, the dataset is not concise enough to allow for a definitive attribution of a Mesozoic origin to other marble sequences than the Vulturese-Belioara Series.

Flood basalts of the Deccan Volcanic Province erupted between about 67.5 to 60.5 Ma ago and reached a thickness of up to 3500 m. The main part consists of compound and simple lava flows with a tholeiitic composition erupted within 500,000 years at about 65 Ma. Within the compound lava flows, vesicles and cavities are frequent. They are filled by secondary minerals partly of well development and large size. This study presents data on the secondary mineralization including detailed field descriptions, optical, cathodoluminescence and SEM microscopy, X-ray diffractometry, fluid inclusions, C and O isotope analyses, and Rb-Sr and K-Ar geochronology. The investigations indicate a multistage precipitation sequence with three main stages. During stage I clay minerals and subsurface filamentous fabrics (SFFs), of probably biogenic origin, formed after the lava flows cooled down near to the Earth&rsquo, s surface. In stage II, first an assemblage of calcite (I) and zeolite (I) (including mordenite, heulandite, and stilbite) as well as plagioclase was overgrown by chalcedony, and finally a second calcite (II) and zeolite (II) generation developed by burial metamorphism by subsequent lava flows. Stage III is characterized by precipitation of a third calcite (III) generation together with powellite and apophyllite from late hydrothermal fluids. Rb-Sr and K-Ar ages of apophyllite indicate a large time span for stage III. Apophyllite formed within different time intervals from the Paleogene to the early Miocene even within individual lava flows at certain localities. From the Savda/Jalgaon quarry complex, ages cluster at 44&ndash, 48 Ma and 25&ndash, 28 Ma, whereas those from the Nashik area are 55&ndash, 58 Ma and 21&ndash, 23 Ma, respectively.

The interaction of water with metal oxides controls their activity and stability in heterogeneous catalysis and electrocatalysis. In this work, we combine density functional theory calculations and infrared reflection absorption spectroscopy (IRAS) to identify the structural motifs formed upon interaction of water with an atomically defined Co

We have investigated the adsorption and dissociation of water and its co-adsorption with CO on atomically defined cobalt oxide nanoislands on Pt(111). The CoO islands were prepared under ultrahigh vacuum (UHV) conditions by reactive deposition of Co metal in oxygen atmosphere. The island structure was characterized by scanning tunneling microscopy (STM), showing that the nanoislands consist of a CoO bilayer and are regularly shaped with island edges that are mainly terminated by Co2+ ions. D2O was dosed in UHV onto the CoO islands on Pt(111) after pre-saturation with CO. D2O dissociation was monitored in situ by isothermal and temperature programmed infrared reflection absorption spectroscopy (IRAS). Isotopic exchange experiments were performed with H2O, D2O, and D2 18O to elucidate the nature of the hydroxyl groups. Three principal types of OD species are identified: (i) isolated OD at the edges of the CoO islands (Co-OeD), (ii) OD groups within larger hydroxylated areas on the CoO islands (Co-OcD), and (iii) isolated OD groups on the CoO terraces (Co-OtD). At 400 K, water adsorbs dissociatively on the CoO islands and forms isolated hydroxyl species (Co-OeD) at the island edges only. At room temperature (300 K), the coverage of hydroxyl groups increases rapidly, in line with the water-assisted hydroxylation reaction suggested previously. Adsorption experiments with D2 18O suggest that two equivalent groups are formed from one water molecule after dissociation at island edges, leading to the formation of larger hydroxylated areas on the CoO islands (Co-OcD) and, in addition, isolated OD species on the CoO terraces (Co-OtD). While the initial step of D2O dissociation is facile, the formation of larger hydroxylated areas is a slow and irreversible process. At 200 K, the formation of hydroxylated areas is accompanied by the co-adsorption of molecular water. The hydroxyl groups on the CoO islands are shown to interact with the CO preadsorbed on the CoO/Pt(111) model system. In particular, we observe a new CO species, stabilized by OD groups on the CoO islands, which adsorbs much stronger than CO on the OD-free CoO surface.

The mechanical characterization of different cell types is important to improve the physiological understanding of cells. Cell types can be differentiated by their elasticity, which is a measure of the amount of deformation under a given stress. Simulations based on the finite element method help us to understand, verify and improve the analysis of deformation-based cell characterization methods such as flow-based cytometry. We achieve efficient computations using a 2D-rotationally symmetric model, based on fluid-structure interaction with a hyper-elastic material. The deformation of a cell along the entirety of a microfluidic channel can be tracked for a variety of elasticities, viscosities, cell sizes, channel geometries and flow rates. The model is even able to simulate soft cells with Young’s modulus of a few hundred pascals in microfluidic channels up to 2 mm in length. Simulations can be carried out in media with constant viscosity as well as in non-Newtonian fluids with shear-dependent viscosity. We have shown that the cell carrier-medium has a strong influence on cell deformation. The position of steady-state deformation dependence on cell properties is investigated. Furthermore, the simulation model can reproduce experimentally observed relaxation of cells, which can then be mapped to actual material parameters to classify and distinguish different cell types.

New Ar–Ar muscovite and Rb–Sr biotite age data in combination with structural analyses from the Apuseni Mountains provide new constraints on the timing and kinematics of deformation during the Cretaceous. Time–temperature paths from the structurally highest basement nappe of the Apuseni Mountains in combination with sedimentary data indicate exhumation and a position close to the surface after the Late Jurassic emplacement of the South Apuseni Ophiolites. Early Cretaceous Ar–Ar muscovite ages from structurally lower parts in the Biharia Nappe System (Dacia Mega-Unit) show cooling from medium-grade conditions. NE–SW-trending stretching lineation and associated kinematic indicators of this deformation phase (D1) are overprinted by top-NW-directed thrusting during D2. An Albian to Turonian age (110–90 Ma) is proposed for the main deformation (D2) that formed the present-day geometry of the nappe stack and led to a pervasive retrograde greenschist-facies overprint. Thermochronological and structural data from the Bihor Unit (Tisza Mega-Unit) allowed to establish E-directed differential exhumation during Early–Late Cretaceous times (D3.1). Brittle detachment faulting (D3.2) and the deposition of syn-extensional sediments indicate general uplift and partial surface exposure during the Late Cretaceous. Brittle conditions persist during the latest Cretaceous compressional overprint (D4). Electronic supplementary material The online version of this article (doi:10.1007/s00531-016-1335-y) contains supplementary material, which is available to authorized users.

Tectono-thermal evolution of the Veporic Unit was revealed by multiple geochronological methods, including 87Rb/86Sr on muscovite and biotite, zircon and apatite fission-track, and apatite (U–Th)/He analysis. Based on the new data, the following Alpine tectono-thermal stages can be distinguished: The Eo-Alpine Cretaceous nappe stacking (~ 135–95 Ma) resulted in burial of the Veporic Unit beneath the northward overthrusting Gemeric Unit and overlying Jurassic Meliata accretionary wedge. During this process the Veporic Unit reached metamorphic peak of greenschist- to amphibolite facies accompanied by orogen-parallel flow in its lower and middle crust. The subsequent evolution of this crust is associated with two distinct exhumation mechanisms related to collision with the northerly Tatric–Fatric basement. The first mechanism (~ 90–80 Ma) is associated with internal subhorizontal shortening of the Veporic Unit reflected by large-scale upright folding and heterogeneous exhumation of the Veporic lower crust in the cores of crustal-scale antiforms. This led to juxtaposition of the higher and lower grade parts of basement, all cooled down to ~ 350 °C by ~ 80 Ma. The second mechanism is associated with the overthrusting of the Veporic Unit over the attenuated Fatric crust. This led to a passive en-block exhumation of the Veporic crust from ~ 350 °C to 60 °C between ~ 80 and 55 Ma followed by erosion (~ 55–35 Ma). The erosion processes resulted in formation of planation surface before the Late Eocene transgression. After erosion and planation, a new sedimentary cycle of the Central Carpathian Palaeogene Basin was deposited with the sedimentary strata thickness of ~ 1.5–2.0 km (~ 21–17 Ma). The early to middle Miocene is characterised by destruction tectonic disintegration and erosion of this basin (~ 20–13 Ma) and formation of the Neogene Vepor Stratovolcano (~ 13 Ma). The final shaping of the area has been linked to erosional processes of the volcanic structure since the Late Sarmatian with accelerated processes during the Plio-Quaternary.

The core of the Alpine orogen in the Eastern Alps (Tauern Window) experienced a change from orogen-normal shortening and post-nappe doming to predominantly orogen-parallel extension and tectonic unroofing during late Oligocene to Miocene northward indentation of the Adriatic Microplate. A new 147 Sm/ 144 Nd isochron age of 25.7 ± 0.9 Ma on a garnet-bearing assemblage from the lowest nappe complex forming a dome in the eastern part of the Tauern Window indicates that high temperatures related to post-nappe Barrovian-type metamorphism overlapped in time with the onset of doming. New 87 Rb/ 87 Sr biotite ages from this same complex combined with previously published 87 Rb/ 87 Sr white mica ages suggest that doming and exhumation began no later than 28 Ma immediately in front of indenting Austroalpine crustal blocks, then migrated laterally to the ESE during rapid exhumation and orogen-parallel stretching beginning at about 23 Ma. Rapid cooling ended at approximately 17 Ma in the footwall of the Katschberg Normal Fault, which delimits the eastern margin of the Tauern Window. A similar pattern of migrating doming, orogen-parallel extension and cooling is recognized in the western part of the Tauern Window, where rapid exhumation began at about 20 Ma, some 2–3 Ma later than in the eastern part. This difference in the onset of rapid exhumation as well as the overall migration of doming from the center to the ends of the Tauern Window are attributed to fragmentation of the aforementioned Austroalpine blocks along the leading edge of the main Adriatic indenter (Southern Alps) as this indenter advanced to the north.

We have studied particle size effects on atomically-defined model catalysts both in ultrahigh vacuum (UHV) and under electrochemical (EC) conditions in liquid electrolytes. The model catalysts were prepared in UHV by physical vapour deposition (PVD) of Pt onto an ordered Co3O4(111) film on Ir(100), yielding nanoparticles (NPs) with an average size from 10 to 500 atoms per particle (0.8 to 3 nm). The model systems were characterized in UHV using surface science methods including scanning tunnelling microscopy (STM), before transferring them out of the UHV and into the electrolyte without contact to ambient conditions. By X-ray photoelectron spectroscopy (XPS) we show that the model surfaces are stable in the EC environment under the applied conditions (0.1 to 1 M phosphate buffer, pH 10, 0.33 to 1.03 VRHE). As a reference, we study Pt(111) under identical conditions. In UHV, we also investigated the adsorption of CO using infrared reflection absorption spectroscopy (IRRAS). Under EC conditions, we performed equivalent experiments using EC infrared reflection absorption spectroscopy (EC-IRRAS) in combination with cyclic voltammetry (CV). Characteristic differences were observed between the IR spectra under EC conditions and in UHV. Besides the red-shift induced by the interfacial electric field (Stark effect), the EC IR bands of CO on Pt(111) show a larger width (by a factor of 2) as a result of local variations in the CO environment and coupling to the electrolyte. The CO IR bands of the Pt NPs are even broader (by a factor of 5), which is attributed to local variations of the interfacial electric field at the NP surface. Further pronounced differences are observed between the spectra taken in UHV and in the electrolyte regarding the site occupation and its dependence on particle size. In UHV, adsorption at on-top sites is preferred on Pt(111) at low coverage and similar adsorption ratios of on-top and bridge-bonded CO are formed at saturation coverage. In sharp contrast, on-top adsorption of CO on Pt(111) is partially suppressed under EC conditions. This effect is attributed to the competitive adsorption of anions from the electrolyte and leads to a clear preference for bridge sites at higher potentials (0.5 VRHE). For the Pt NPs, the situation is different and an increasing fraction of on-top CO is observed with decreasing particle size, both under EC conditions and in UHV. For the smallest particles (10-20 atoms) we do not detect any bridge-bonded CO. This change in site preference as a function of particle size is attributed to stronger on-top adsorption on low-coordinated Pt atoms of small Pt NPs. The effect leads to a clear preference for on-top adsorption in the electrolyte even at low CO coverage and over the full potential range studied.

Catalysis letters 148(9), 2901 - 2910 (2018). doi:10.1007/s10562-018-2487-0, Liquid organic hydrogen carriers (LOHCs) have great potential as a hydrogen storage medium needed for a future sustainable energy system. Dehydrogenation of LOHCs requires a catalyst, such as supported Pd nanoparticles. Under reaction conditions, hydrogen and carbon may diffuse into the bulk of supported Pd catalyst particles and affect their activity and selectivity. The detailed understanding of this process is critical for the use of LOHCs in future hydrogen storage technologies. In this work, we studied these processes in-situ on a Pd model catalyst using high-energy grazing incidence X-ray diffraction. Pd nanoparticles were evaporated in ultra-high vacuum on a polished $α$-Al$_2$O$_3$(0001) substrate. The particles, with an initial average size of ~ 3.4 nm, were investigated at elevated temperature during their interaction with H$_2$ and methylcyclohexane (MCH) representing a model LOHC. The interaction with H$_2$ was studied in-situ at partial pressures up to 1 bar and temperatures between 300 and 500 K. At 300 K, the Pd nanoparticles (NPs) show a transition from $α$-PdH to $β$-PdH as a function of the H$_2$ pressure. The transition occurs gradually, which is attributed to the heterogeneity of the NP system. The hydrogen uptake in $β$-PdH$_x$ at 300 K and 1 bar is estimated to be XH ~ 0.37 ± 0.03 indicating that the miscibility gap is narrowed for the nanoparticular system. With increasing temperature, X$_H$ decreases until no $β$-PdH phase is formed anymore at 500 K. At the same temperature, we studied the interaction of the Pd/sapphire model catalyst with MCH, both in the presence and in the absence of H$_2$. In the absence of H$_2$, carbon is formed and diffuses into the bulk yielding PdC$_x$ with a C concentration of around x ~ 0.05 ± 0.01. In the presence of H$_2$ in the gas phase, bulk carbon formation in the Pd/sapphire model catalyst is completely suppressed. These results show that Pd nanoparticles act as an adequate catalyst for the dehydrogenation of MCH., Published by Springer Science + Business Media B.V, Dordrecht [u.a.]