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.

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.

In Situ Surface-Sensitive Investigation of Multiple Carbon Phases on Fe(110) in the Fischer-Tropsch Synthesis.

Carbide formation on iron-based catalysts is an integral and, arguably, the most important part of the Fischer-Tropsch synthesis process, converting CO and H2 into synthetic fuels and numerous valuable chemicals. Here, we report an in situ surface-sensitive study of the effect of pressure, temperature, time, and gas feed composition on the growth dynamics of two distinct iron-carbon phases with the octahedral and trigonal prismatic coordination of carbon sites on an Fe(110) single crystal acting as a model catalyst. Using a combination of state-of-the-art X-ray photoelectron spectroscopy at an unprecedentedly high pressure, high-energy surface X-ray diffraction, mass spectrometry, and theoretical calculations, we reveal the details of iron surface carburization and product formation under semirealistic conditions. We provide a detailed insight into the state of the catalyst's surface in relation to the reaction.

Atomic scale step structure and orientation of a curved surface ZnO single crystal.

We have investigated the surface structure of a curved ZnO-crystal, going from the (0001)-facet at 0° miscut to the (101¯4)-facet at a miscut of 24.8° using scanning tunneling microscopy and low energy electron diffraction. We find that the surface separates locally into (0001)-terraces and (101¯4)-facets, where the ratio between the facets depends on the miscut angle. In X-ray photoemission spectroscopy (XPS) the intensity of an O 1s component scaling with the step density of the surface is observed. No other facets were observed and the surface maintains a high degree of order over all angles. Such a curved ZnO crystal can be used for systematic studies relating the step density to the chemical reactivity using XPS to probe the curved surface at different positions.

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.

Interaction of a tripeptide with titania surfaces: RGD adsorption on rutile TiO2(110) and model dental implant surfaces.

The adsorption of peptides on metal oxides is an area of significant interest, both fundamentally and in a number of technologically important areas. These range from the integration of biomaterials in the body, to denaturation of protein therapeutics and the use of biomolecules and bioinspired materials in synthesis and stabilization of novel nanomaterials. Here we present a study of the tripeptide arginylglycylaspartic acid (RGD) on the surfaces of vacuum-prepared single crystalline TiO2(110), pyrocatechol-capped TiO2(110), and model SLA and SLActive dental implant samples. X-ray Photoelectron Spectroscopy and Scanning Tunneling Microscopy show that the RGD adsorption mode on the single crystal is consistent with bonding through the deprotonated carboxylate groups of the peptide to surface Ti atoms of the substrate. Despite the increased hydrophobicity of the pyrocatechol-capped TiO2(110) surface RGD adsorption from solution increases following this surface treatment. RGD adsorption on SLA and SLActive surfaces shows that the SLActive surface has a greater uptake of RGD. The RGD uptake on the pyrocatechol capped single crystal and the model implant surfaces suggest that the ease with which surface contaminant hydrocarbons are removed from the surface has a greater influence on peptide adsorption than hydrophobicity/hydrophilicity of the surface.

Versailles Project on Advanced Materials and Standards Interlaboratory Study on Measuring the Thickness and Chemistry of Nanoparticle Coatings Using XPS and LEIS.

We report the results of a VAMAS (Versailles Project on Advanced Materials and Standards) inter-laboratory study on the measurement of the shell thickness and chemistry of nanoparticle coatings. Peptide-coated gold particles were supplied to laboratories in two forms: a colloidal suspension in pure water and; particles dried onto a silicon wafer. Participants prepared and analyzed these samples using either X-ray photoelectron spectroscopy (XPS) or low energy ion scattering (LEIS). Careful data analysis revealed some significant sources of discrepancy, particularly for XPS. Degradation during transportation, storage or sample preparation resulted in a variability in thickness of 53 %. The calculation method chosen by XPS participants contributed a variability of 67 %. However, variability of 12 % was achieved for the samples deposited using a single method and by choosing photoelectron peaks that were not adversely affected by instrumental transmission effects. The study identified a need for more consistency in instrumental transmission functions and relative sensitivity factors, since this contributed a variability of 33 %. The results from the LEIS participants were more consistent, with variability of less than 10 % in thickness and this is mostly due to a common method of data analysis. The calculation was performed using a model developed for uniform, flat films and some participants employed a correction factor to account for the sample geometry, which appears warranted based upon a simulation of LEIS data from one of the participants and comparison to the XPS results.

Ionic Liquid Ordering at an Oxide Surface.

The interaction of the ionic liquid [C4 C1 Im][BF4 ] with anatase TiO2 , a model photoanode material, has been studied using a combination of synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The system is of interest as a model for fundamental electrolyte-electrode and dye-sensitized solar cells. The initial interaction involves degradation of the [BF4 ]- anion, resulting in incorporation of F into O vacancies in the anatase surface. At low coverages, [C4 C1 Im][BF4 ] is found to order at the anatase(101) surface via electrostatic attraction, with the imidazolium ring oriented 32±4° from the anatase TiO2 surface. As the coverage of ionic liquid increases, the influence of the oxide surface on the topmost layers is reduced and the ordering is lost.

Adsorption studies of p-aminobenzoic acid on the anatase TiO2(101) surface.

The adsorption of p-aminobenzoic acid (pABA) on the anatase TiO2(101) surface has been investigated using synchrotron radiation photoelectron spectroscopy, near edge X-ray absorption fine structure (NEXAFS) spectroscopy, and density functional theory (DFT). Photoelectron spectroscopy indicates that the molecule is adsorbed in a bidentate mode through the carboxyl group following deprotonation. NEXAFS spectroscopy and DFT calculations of the adsorption structures indicate the ordering of a monolayer of the amino acid on the surface with the plane of the ring in an almost upright orientation. The adsorption of pABA on nanoparticulate TiO2 leads to a red shift of the optical absorption relative to bare TiO2 nanoparticles. DFT and valence band photoelectron spectroscopy suggest that the shift is attributed to the presence of the highest occupied molecular orbitals in the TiO2 band gap region and the presence of new molecularly derived states near the foot of the TiO2 conduction band.