Photoinduced Dynamics at the Water/TiO_{2}(101) Interface.

We present a femtosecond time-resolved optical pump-soft x-ray probe photoemission study in which we follow the dynamics of charge transfer at the interface of water and anatase TiO_{2}(101). By combining our observation of transient oxygen O 1s core level peak shifts at submonolayer water coverages with Ehrenfest molecular dynamics simulations we find that ultrafast interfacial hole transfer from TiO_{2} to molecularly adsorbed water is completed within the 285 fs time resolution of the experiment. This is facilitated by the formation of a new hydrogen bond between an O_{2c} site at the surface and a physisorbed water molecule. The calculations fully corroborate our experimental observations and further suggest that this process is preceded by the efficient trapping of the hole at the surface of TiO_{2} by hydroxyl species (-OH), that form following the dissociative adsorption of water. At a water coverage exceeding a monolayer, interfacial charge transfer is suppressed. Our findings are directly applicable to a wide range of photocatalytic systems in which water plays a critical role.

Metastability of palladium carbide nanoparticles during hydrogen release from liquid organic hydrogen carriers.

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-Al2O3(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 PdxC phase followed by its conversion to Pd6C. The dynamic stability of the Pd6C 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 Pd6C phase is dynamically stable under low flow rate of reactants. At the high reactant flow, the Pd6C 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, PdxC and Pd6C. Formation and decomposition of Pd6C proceeds via a PdxC 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 Pd6C and PdxC phases is an intrinsic phenomenon in LOHC dehydrogenation on Pd-based catalysts and strongly depends on particle size and reaction conditions.

Interaction of Water with Graphene/Ir(111) Studied by Vibrational Spectroscopy.

Water in confinement exhibits altered properties in molecular arrangement, bonding, and interaction with its neighboring environment, as compared to its bulk counterpart. In this work, periodically arranged D2O nano droplets of ∼1 nm size on top of a graphene/iridium moiré superstructure were investigated by Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) under ultrahigh vacuum conditions at ∼120 K. The IR bands of D2O clusters differ significantly from those observed for bulk D2O amorphous solid water or crystalline ice phases. Blue-shifted symmetric and asymmetric stretching bands with narrower band widths and modified band intensity ratios were observed, pointing to an enhanced internal order and a reduced nearest neighbor distance. Furthermore, two IR bands of "dangling" deuterium atoms were detected originating from threefold coordinated water molecules at the surface of the clusters and at their interface to the graphene layer. The latter arose only with the transition from the water clusters to an amorphous solid water layer. We propose that upon coalescence, opposing local dipoles trigger a hydrogen bond rearrangement at the interface. Our results represent a first step toward an atomistic understanding of water in confinement.

Modulating the Mechanical Properties of Supercrystalline Nanocomposite Materials via Solvent-Ligand Interactions.

Supercrystalline nanocomposite materials with micromechanical properties approaching those of nacre or similar structural biomaterials can be produced by self-assembly of organically modified nanoparticles and further strengthened by cross-linking. The strengthening of these nanocomposites is controlled via thermal treatment, which promotes the formation of covalent bonds between interdigitated ligands on the nanoparticle surface. In this work, it is shown how the extent of the mechanical properties enhancement can be controlled by the solvent used during the self-assembly step. We find that the resulting mechanical properties correlate with the Hansen solubility parameters of the solvents and ligands used for the supercrystal assembly: the hardness and elastic modulus decrease as the Hansen solubility parameter of the solvent approaches the Hansen solubility parameter of the ligands that stabilize the nanoparticles. Moreover, it is shown that self-assembled supercrystals that are subsequently uniaxially pressed can deform up to 6 %. The extent of this deformation is also closely related to the solvent used during the self-assembly step. These results indicate that the conformation and arrangement of the organic ligands on the nanoparticle surface not only control the self-assembly itself but also influence the mechanical properties of the resulting supercrystalline material. The Hansen solubility parameters may therefore serve as a tool to predict what solvents and ligands should be used to obtain supercrystalline materials with good mechanical properties.

Organically linked iron oxide nanoparticle supercrystals with exceptional isotropic mechanical properties.

It is commonly accepted that the combination of the anisotropic shape and nanoscale dimensions of the mineral constituents of natural biological composites underlies their superior mechanical properties when compared to those of their rather weak mineral and organic constituents. Here, we show that the self-assembly of nearly spherical iron oxide nanoparticles in supercrystals linked together by a thermally induced crosslinking reaction of oleic acid molecules leads to a nanocomposite with exceptional bending modulus of 114 GPa, hardness of up to 4 GPa and strength of up to 630 MPa. By using a nanomechanical model, we determined that these exceptional mechanical properties are dominated by the covalent backbone of the linked organic molecules. Because oleic acid has been broadly used as nanoparticle ligand, our crosslinking approach should be applicable to a large variety of nanoparticle systems.

Model Catalytic Studies of Novel Liquid Organic Hydrogen Carriers: Indole, Indoline and Octahydroindole on Pt(111).

Indole derivatives were recently proposed as potential liquid organic hydrogen carriers (LOHC) for storage of renewable energies. In this work, we have investigated the adsorption, dehydrogenation and degradation mechanisms in the indole/indoline/octahydroindole system on Pt(111). We have combined infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS) and DFT calculations. Indole multilayers show a crystallization transition at 200 K, in which the molecules adopt a strongly tilted orientation, before the multilayer desorbs at 220 K. For indoline, a less pronounced restructuring transition occurs at 150 K and multilayer desorption is observed at 200 K. Octahydroindole multilayers desorb already at 185 K, without any indication for restructuring. Adsorbed monolayers of all three compounds are stable up to room temperature and undergo deprotonation at the NH bond above 300 K. For indoline, the reaction is followed by partial dehydrogenation at the 5-membered ring, leading to the formation of a flat-lying di-σ-indolide in the temperature range from 330-390 K. Noteworthy, the same surface intermediate is formed from indole. In contrast, the reaction of octahydroindole with Pt(111) leads to the formation of a different intermediate, which originates from partial dehydrogenation of the 6-membered ring. Above 390 K, all three compounds again form the same strongly dehydrogenated and partially decomposed surface species.

Low-temperature oxidation of carbon monoxide with gold(III) ions supported on titanium oxide.

Au/TiO2 catalysts prepared by a deposition-precipitation process and used for CO oxidation without previous calcination exhibited high, largely temperature-independent conversions at low temperatures, with apparent activation energies of about zero. Thermal treatments, such as He at 623 K, changed the conversion-temperature characteristics to the well-known S-shape, with activation energies slightly below 30 kJ mol(-1). Sample characterization by XAFS and electron microscopy and a low-temperature IR study of CO adsorption and oxidation showed that CO can be oxidized by gas-phase O2 at 90 K already over the freeze-dried catalyst in the initial state that contained Au exclusively in the +3 oxidation state. CO conversion after activation in the feed at 303 K is due to Au(III)-containing sites at low temperatures, while Au(0) dominates conversion at higher temperatures. After thermal treatments, CO conversion in the whole investigated temperature range results from sites containing exclusively Au(0).

Multifunctional, defect-engineered metal-organic frameworks with ruthenium centers: sorption and catalytic properties.

A mixed-linker solid-solution approach was employed to modify the metal sites and introduce structural defects into the mixed-valence Ru(II/III) structural analogue of the well-known MOF family [M3(II,II)(btc)2] (M=Cu, Mo, Cr, Ni, Zn; btc=benzene-1,3,5-tricarboxylate), with partly missing carboxylate ligators at the Ru2 paddle-wheels. Incorporation of pyridine-3,5-dicarboxylate (pydc), which is the same size as btc but carries lower charge, as a second, defective linker has led to the mixed-linker isoreticular derivatives of Ru-MOF, which display characteristics unlike those of the defect-free framework. Along with the creation of additional coordinatively unsaturated sites, the incorporation of pydc induces the partial reduction of ruthenium. Accordingly, the modified Ru sites are responsible for the activity of the "defective" variants in the dissociative chemisorption of CO2, the enhanced performance in CO sorption, the formation of hydride species, and the catalytic hydrogenation of olefins.

Light-Induced Transformation of Virus-Like Particles on TiO2.

Titanium dioxide (TiO2) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO2 surface. The in situ GISAXS measurements under an N2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

Iron metal-organic frameworks MIL-88B and NH2-MIL-88B for the loading and delivery of the gasotransmitter carbon monoxide.

Crystals of MIL-88B-Fe and NH2-MIL-88B-Fe were prepared by a new rapid microwave-assisted solvothermal method. High-purity, spindle-shaped crystals of MIL-88B-Fe with a length of about 2 µm and a diameter of 1 µm and needle-shaped crystals of NH2-MIL-88B-Fe with a length of about 1.5 µm and a diameter of 300 nm were produced with uniform size and excellent crystallinity. The possibility to reduce the as-prepared frameworks and the chemical capture of carbon monoxide in these materials was studied by in situ ultrahigh vacuum Fourier-transform infrared (UHV-FTIR) spectroscopy and Mössbauer spectroscopy. CO binding occurs to unsaturated coordination sites (CUS). The release of CO from the as-prepared materials was studied by a myoglobin assay in physiological buffer. The release of CO from crystals of MIL-88B-Fe with t(1/2) = 38 min and from crystals of NH2-MIL-88B-Fe with t(1/2) = 76 min were found to be controlled by the degradation of the MIL materials under physiological conditions. These MIL-88B-Fe and NH2-MIL-88B-Fe materials show good biocompatibility and have the potential to be used in pharmacological and therapeutic applications as carriers and delivery vehicles for the gasotransmitter carbon monoxide.

A combined experimental and computational study on the adsorption and reactions of NO on rutile TiO2.

In this work we combined computational density functional theory with experimental infrared spectroscopy to determine the adsorbate structure of NO and its reaction products N(2)O(2), N(2)O, and NO(2) on rutile TiO(2). These reactions are important for the photo-catalytic reduction of NO in exhaust gas, but yet little is known about the mechanisms or the intermediates involved. The combination of high-quality ultrahigh vacuum FTIRS data with large scale embedded cluster calculations using an accurate hybrid density functional rendered it possible to identify and assign unambiguously vibrational frequencies for nine species which are formed upon adsorption and reaction of NO on rutile TiO(2). Some of them have been observed for the first time. As a result of the quantum chemical calculations we can report for all adsorbates accurate structures and binding energies.

Solvent controlled 2D structures of bottom-up fabricated nanoparticle superlattices.

We demonstrate that oleyl phosphate ligand-stabilized iron oxide nanocubes as building blocks can be assembled into 2D supercrystalline mono- and multilayers on flat YSZ substrates within a few minutes using a simple spin-coating process. As a bottom-up process, the growth takes place in a layer-by-layer mode and therefore by tuning the spin-coating parameters, the exact number of deposited monolayers can be controlled. Furthermore, ex situ scanning electron and atomic force microscopy as well as X-ray reflectivity measurements give evidence that the choice of solvent allows the control of the lattice type of the final supercrystalline monolayers. This observation can be assigned to the different Hansen solubilities of the solvents used for the nanoparticle dispersion because it determines the size and morphology of the ligand shell surrounding the nanoparticle core. Here, by using toluene and chloroform as solvents, it can be controlled whether the resulting monolayers are ordered in a square or hexagonal supercrystalline lattice.

Diblock copolymer pattern protection by silver cluster reinforcement.

Pattern fabrication by self-assembly of diblock copolymers is of significant interest due to the simplicity in fabricating complex structures. In particular, polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) is a fascinating base material as it forms an ordered micellar structure on silicon surfaces. In this work, silver (Ag) is applied using direct current magnetron sputter deposition and high-power impulse magnetron sputter deposition on an ordered micellar PS-b-P4VP layer. The fabricated hybrid materials are structurally analyzed by field emission scanning electron microscopy, atomic force microscopy, and grazing incidence small angle X-ray scattering. When applying simple aqueous posttreatment, the pattern is stable and reinforced by Ag clusters, making micellar PS-b-P4VP ordered layers ideal candidates for lithography.

Adsorption and Inactivation of SARS-CoV-2 on the Surface of Anatase TiO2(101).

We investigated the adsorption of severe acute respiratory syndrome corona virus 2 (SARS-CoV-2), the virus responsible for the current pandemic, on the surface of the model catalyst TiO2(101) using atomic force microscopy, transmission electron microscopy, fluorescence microscopy, and X-ray photoelectron spectroscopy, accompanied by density functional theory calculations. Three different methods were employed to inactivate the virus after it was loaded on the surface of TiO2(101): (i) ethanol, (ii) thermal, and (iii) UV treatments. Microscopic studies demonstrate that the denatured spike proteins and other proteins in the virus structure readsorb on the surface of TiO2 under thermal and UV treatments. The interaction of the virus with the surface of TiO2 was different for the thermally and UV treated samples compared to the sample inactivated via ethanol treatment. AFM and TEM results on the UV-treated sample suggested that the adsorbed viral particles undergo damage and photocatalytic oxidation at the surface of TiO2(101) which can affect the structural proteins of SARS-CoV-2 and denature the spike proteins in 30 min. The role of Pd nanoparticles (NPs) was investigated in the interaction between SARS-CoV-2 and TiO2(101). The presence of Pd NPs enhanced the adsorption of the virus due to the possible interaction of the spike protein with the NPs. This study is the first investigation of the interaction of SARS-CoV-2 with the surface of single crystalline TiO2(101) as a potential candidate for virus deactivation applications. Clarification of the interaction of the virus with the surface of semiconductor oxides will aid in obtaining a deeper understanding of the chemical processes involved in photoinactivation of microorganisms, which is important for the design of effective photocatalysts for air purification and self-cleaning materials.

Surface structure of magnetite (111) under oxidizing and reducing conditions.

We report on differences in the magnetite (111) surface structure when prepared under oxidizing and reducing conditions. Both preparations were done under UHV conditions at elevated temperatures, but in one case the sample was cooled down while keeping it in an oxygen atmosphere. Scanning tunneling microscopy after each of the preparations showed a different apparent morphology, which is discussed to be an electronic effect and which is reflected in the necessity of using opposite bias tunneling voltages in order to obtain good images. Surface x-ray diffraction revealed that both preparations lead to Fe vacancies, leading to local O-terminations, the relative fraction of which depending on the preparation. The preparation under reducing conditions lead to a larger fraction of Fe-termination. The geometric structure of the two different terminations was found to be identical for both treatments, even though the surface and near-surface regions exhibit small compositional differences; after the oxidizing treatment they are iron deficient. Further evidence for the dependence of iron vs oxygen fractional surface terminations on preparation conditions comes from Fourier transform infrared reflection-absorption spectroscopy, which is used to study the adsorption of formic acid. These molecules dissociate and adsorb in chelating and bidentate bridging geometries on the Fe-terminated areas and the signal of typical infrared absorption bands is stronger after the preparation under reducing conditions, which results in a higher fraction of Fe-termination. The adsorption of formic acid induced an atomic roughening of the magnetite (111) surface which we conclude from the quantitative analysis of the crystal truncation rod data. The roughening process is initiated by atomic hydrogen, which results from the dissociation of formic acid after its adsorption on the surface. Atomic hydrogen adsorbs at surface oxygen and after recombination with another H this surface hydroxyl can form H2O, which may desorb from the surface, while iron ions diffuse into interstitial sites in the bulk.

Adsorption of oleic acid on magnetite facets.

The microscopic understanding of the atomic structure and interaction at carboxylic acid/oxide interfaces is an important step towards tailoring the mechanical properties of nanocomposite materials assembled from metal oxide nanoparticles functionalized by organic molecules. We have studied the adsorption of oleic acid (C17H33COOH) on the most prominent magnetite (001) and (111) crystal facets at room temperature using low energy electron diffraction, surface X-ray diffraction and infrared vibrational spectroscopy complemented with molecular dynamics simulations used to infer specific hydrogen bonding motifs between oleic acid and oleate. Our experimental and theoretical results give evidence that oleic acid adsorbs dissociatively on both facets at lower coverages. At higher coverages, the more pronounced molecular adsorption causes hydrogen bond formation between the carboxylic groups, leading to a more upright orientation of the molecules on the (111) facet in conjunction with the formation of a denser layer, as compared to the (001) facet. This is evidenced by the C=O double bond infrared line shape, in depth molecular dynamics bond angle orientation and hydrogen bond analysis, as well as X-ray reflectivity layer electron density profile determination. Such a higher density can explain the higher mechanical strength of nanocomposite materials based on magnetite nanoparticles with larger (111) facets.

Strengthening Engineered Nanocrystal Three-Dimensional Superlattices via Ligand Conformation and Reactivity.

Nanocrystal assembly into ordered structures provides mesostructural functional materials with a precise control that starts at the atomic scale. However, the lack of understanding on the self-assembly itself plus the poor structural integrity of the resulting supercrystalline materials still limits their application into engineered materials and devices. Surface functionalization of the nanobuilding blocks with organic ligands can be used not only as a means to control the interparticle interactions during self-assembly but also as a reactive platform to further strengthen the final material via ligand cross-linking. Here, we explore the influence of the ligands on superlattice formation and during cross-linking via thermal annealing. We elucidate the effect of the surface functionalization on the nanostructure during self-assembly and show how the ligand-promoted superlattice changes subsequently alter the cross-linking behavior. By gaining further insights on the chemical species derived from the thermally activated cross-linking and its effect in the overall mechanical response, we identify an oxidative radical polymerization as the main mechanism responsible for the ligand cross-linking. In the cascade of reactions occurring during the surface-ligands polymerization, the nanocrystal core material plays a catalytic role, being strongly affected by the anchoring group of the surface ligands. Ultimately, we demonstrate how the found mechanistic insights can be used to adjust the mechanical and nanostructural properties of the obtained nanocomposites. These results enable engineering supercrystalline nanocomposites with improved cohesion while preserving their characteristic nanostructure, which is required to achieve the collective properties for broad functional applications.

Hydrogen Solubility and Atomic Structure of Graphene Supported Pd Nanoclusters.

We investigated the atomic structure of graphene supported Pd nanoclusters and their interaction with hydrogen up to atmospheric pressures at room temperature by surface X-ray diffraction and scanning tunneling microscopy. We find that Ir seeded Pd nanocluster superlattices with 1.2 nm cluster diameters can be grown on the graphene/Ir(111) moiré template with high structural perfection. The superlattice clusters are anchored through the rehybridized graphene to the Ir support, which superimposes a 2.0% inplane compression onto the clusters. During hydrogen exposure at 10 mbar pressure and room temperature, a significant part of the clusters gets unpinned from the superlattice. The clusters in registry undergo an out-of-plane expansion only, whereas the detached clusters expand in in- and out-of-plane directions. The formation of a hydrogen rich PdHx α' phase was not observed. After exposure to 1 bar, the majority of the clusters are unpinned from superlattice sites, due to their surface interaction with hydrogen and possible spill over to the graphene support. Only minor sintering was observed, which is more pronounced for the unpinned clusters. The results give evidence that ultrasmall Pd clusters on graphene are a stable hydrogen storage system with reduced hydrogen storage hysteresis and maintain a large surface area for hydrogen chemisorption.

Temperature-dependent near-surface interstitial segregation in niobium.

Niobium's superconducting properties are affected by the presence and precipitation of impurities in the near-surface region. A systematic wide-temperature range x-ray diffraction study is presented addressing the effect of low temperatures (108 K-130 K) and annealing treatments (523 K in nitrogen atmosphere, 400 K in UHV) on the near-surface region of a hydrogen-loaded Nb(100) single-crystal. Under these conditions, the response of the natural surface oxides (Nb2O5, NbO2, and NbO) and the changes in the subsurface concentration of interstitial species in Nb are explored, thereby including the cryogenic temperature regime relevant for device operation. The formation and suppression of niobium hydrides in such conditions are also investigated. These treatments are shown to result in: (i) an increase in the concentration of interstitial species (oxygen and nitrogen) occupying the octahedral sites of the Nb bcc lattice at room temperature, both in the near-surface region and in the bulk. (ii) A decrease in the concentration of interstitials within the first 10 nm from the surface at 130 K. (iii) Hydride formation suppression at temperatures as low as 130 K. These results show that mild annealing in nitrogen atmosphere can suppress the formation of superconducting-detrimental niobium hydrides, while subsurface interstitial atoms tend to segregate towards the surface at 130 K, therefore altering the local concentration of impurities within the RF penetration depth of Nb. These processes are discussed in the context of the improvement of niobium superconducting radio-frequency cavities for next-generation particle accelerators.

Heterogeneous Adsorption and Local Ordering of Formate on a Magnetite Surface.

We report a novel heterogeneous adsorption mechanism of formic acid on the magnetite (111) surface. Our experimental results and density functional theory (DFT) calculations give evidence for dissociative adsorption of formic acid in quasibidentate and chelating geometries. The latter is induced by the presence of iron vacancies at the surface, making oxygen atoms accessible for hydrogen atoms from dissociated formic acid. DFT calculations predict that both adsorption geometries are energetically favorable under our experimental conditions. The calculations prove that the locally observed (√3 × âˆš3)R 30° superstructure consists of three formate molecules in a triangular arrangement, adsorbed predominantly in a chelating geometry. The results show how defects can stabilize alternative adsorption geometries, which is a crucial ingredient for a detailed atomistic understanding of reaction barriers on magnetite and other oxide surfaces, as well as for the stability of carboxylic acid based nanocomposite materials.