The beamline for advanced dichroism of the Istituto Officina dei Materiali-Consiglio Nazionale delle Ricerche, operating at the Elettra synchrotron in Trieste (Italy), works in the extreme ultraviolet-soft x-ray photon energy range with selectable light polarization, high energy resolution, brilliance, and time resolution. The beamline offers a multi-technique approach for the investigation of the electronic, chemical, structural, magnetic, and dynamical properties of materials. Recently, one of the three end stations has been dedicated to experiments based on electron transfer processes at the solid/liquid interfaces and during photocatalytic or electrochemical reactions. Suitable cells to perform soft x-ray spectroscopy in the presence of liquids and reagent gases at ambient pressure were developed. Here, we present two types of static cells working in transmission or in fluorescence yield and an electrochemical flow cell that allows us to carry out cyclic voltammetry in situ and electrodeposition on a working electrode and to study chemical reactions under operando conditions. Examples of x-ray absorption spectroscopy measurements performed under ambient conditions and during electrochemical experiments in liquids are presented.

The relation between morphology and energy level alignment in carbon nanotubes (CNT) is a crucial information for the optimization of applications in nanoelectronics, optics, mechanics and (bio)chemistry. Here we present a study of the relation between the electronic properties and the morphology of single wall CNT (SWCNT), aligned multi wall CNT (MWCNT) and unaligned MWCNT. The CNT were synthesized via catalytic chemical vapor deposition in ultra-high vacuum conditions. Combined ultraviolet photoemission and inverse photoemission (IPES) spectra reveal a high sensitivity to the nanotube morphology. In the case of unaligned SWCNT the distinctive unoccupied Van Hove singularities (vHs) features are observed in the high resolution IPES spectra. Those features are assigned to semiconducting and metallic SWCNT states, according to calculated vHs DOS. The two MWCNT samples are similar in the diameter of the tube (about 15 nm) and present similar filled and empty electronic states, although the measured features in the aligned MWCNT are more defined. Noteworthy, interlayer states are also revealed. Their intensities are directly related to the MWCNT alignment. Focussing and geometrical effects associated to the MWCNT alignment are discussed to account the spectral differences.

Hexagonal molybdenum trioxide (h-MoO3) microrods and their composites with graphite, graphene and graphene oxide (GO) are successfully synthesized by a soft chemistry route. The structural, compositional and electronic characteristics of the samples, investigated by a wide range of experimental techniques, evidence that the properties of the carbon material are preserved while yielding phase pure, highly crystalline oxide microstructures. h-MoO3 graphene and GO composites show excellent performance as Li ion batteries (LIBs) anodes. Precisely, h-MoO3 - GO electrodes deliver a remarkable specific capacity of 789 mA h g - 1 after 100 cycles at a high current density of 1000 mA g - 1, while h-MoO3 - graphene electrodes show an excellent stability at very high current densities, with specific capacities of 665 mA h g - 1 and 490 mA h g - 1 at 2000 and 3000 mA g - 1. The uniformly dispersed graphene and GO layers increase the structural stability of the composites and create a conductive network ensuring effective ambipolar diffusion of electrons and Li+ ions, as revealed by electrochemical impedance spectroscopy measurements and scanning electron microscopy of the cycled electrodes. These results expand the potential applications of h-MoO3 composites towards LIBs, paving the way for future improvements in this energy storage field.

Graphene nanoribbons (GNRs) are at the frontier of research on graphene materials since the 1D quantum confinement of electrons allows for the opening of an energy gap. GNRs of uniform and well-defined size and shape can be grown using the bottom-up approach, i.e. by surface assisted polymerization of aromatic hydrocarbons. Since the electronic properties of the nanostructures depend on their width and on their edge states, by careful choice of the precursor molecule it is possible to design GNRs with tailored properties. A key issue for their application in nanoelectronics is their stability under operative conditions. Here, we characterize pristine and oxygen-exposed 1.0 nm wide GNRs with a well-defined mixed edge-site sequence (two zig-zag and one armchair) synthesized on Ag(110) from 1,6-dibromo-pyrene precursors. The energy gap and the presence of quantum confined states are investigated by scanning tunneling spectroscopy. The effect of oxygen exposure under ultra-high vacuum conditions is inferred from scanning tunneling microscopy images and photoemission spectra. Our results demonstrate that oxygen exposure deeply affects the overall system by interacting both with the nanoribbons and with the substrate; this factor must be considered for supported GNRs under operative conditions.

Two different synthetic pathways, namely the miniemulsion and hydrothermal approaches, were investigated for the preparation of silver sulfide nanoparticles, also doped with lanthanide ions. It was demonstrated that the synthesis and the choice of the precursors play a fundamental role in determining the crystalline purity, the size, the stability and the functional properties of the AgS nanostructures. The miniemulsion approach leads to the formation of the targeted structures already at room temperature, but the hydrothermal approach yields particles with increased purity and long-term stability against oxidation. Synchrotron XPS performed with different penetration depths evidences the presence of a stable core of the crystallites composed uniquely of AgS and an external shell where residual elemental S demonstrates the first stage of oxidation due to atmospheric exposure. The samples prepared via hydrothermal synthesis also show a high optical density (0.377) and a good laser-to-heat conversion efficiency (29%).

Combining experimental and ab initio core-level photoelectron spectroscopy (periodic DFT and quantum chemistry calculations), we elucidated how ammonia molecules bond to the hydroxyls of the (H,OH)-Si(001) model surface at a temperature of 130 K. Indeed, theory evaluated the magnitude and direction of the N 1s (and O 1s) chemical shifts according to the nature (acceptor or donor) of the hydrogen bond and, when confronted to experiment, showed unambiguously that the probe molecule makes one acceptor and one donor bond with a pair of hydroxyls. The consistency of our approach was proved by the fact that the identified adsorption geometries are precisely those that have the largest binding strength to the surface, as calculated by periodic DFT. Real-time core-level photoemission enabled measurement of the adsorption kinetics of H-bonded ammonia and its maximum coverage (0.37 ML) under 1.5 x 10(-9) mbar. Experimental desorption free energies were compared to the magnitude of the adsorption energies provided by periodic DFT calculations. Minority species were also detected on the surface. As in the case of H-bonded ammonia, DFT core-level calculations were instrumental to attribute these minority species to datively bonded ammonia molecules, associated with isolated dangling bonds remaining on the surface, and to dissociated ammonia molecules, resulting largely from beam damage.

With the aim of probing the influence of the highly oxidizable selenium in the electrochemically inactive cathode Li2MnO3 material, samples were prepared with selenium substitution in the manganese coordination according to the general formula of Li2Mn1-xSexO3. In Li-ion batteries, oxygen instabilities are one of the major problems confronted that effect the performances of the cathode materials. The crystal and electronic structure properties of the materials were studied with x-ray absorption techniques. Selenium atoms were determined to build Li2SeO4 crystal and due to the oxygen removal during sample preparation mechanisms were determined to cause lower ionic conductivity than the parent Li2MnO3 oxide. The atomic distances in the materials were determined by the fits performed by the commercial code FEFF 8.2. Li2SeO4 crystal was determined as stacked between manganese and lithium atoms and isolated with each other.

The different occupancy of electronic orbitals, the so-called orbital polarization, is a key parameter determining electric and magnetic properties of materials. Here we report on the demonstration of in operando voltage-controlled tuning of the orbital occupation in LaNiO3 epitaxial thin films grown on piezoelectric substrates. The different static contributions to the orbital occupation are disentangled, namely the epitaxial strain and the surface symmetry breaking, and the superimposed electric-field controlled orbital polarization are determined by x-ray linear dichroism at the Ni L-2,L-3 edges. The voltage-controlled orbital polarization allows changing the orbital polarization by about an additional 50%.

Zeolite Y was synthesized and modified with EDTA dealumination procedure. The modified zeolites were analyzed by X-ray diffraction, X-ray absorption spectroscopy, chemical analysis and water adsorption measurements. We demonstrated that dealumination with bulk organic acid such as EDTA is able to reduce the original intense water affinity. Furthermore, it was found that dealumination with EDTA, in contrast with steaming and HCl dealumination, provides fully controllable, predictable and secure process of Al removal from the zeolites' frameworks. The shift of the adsorption isotherm in the low partial pressure range represents an interesting result for adsorption-based applications.

the project AHEAD2020 has been approved within HORIZON 2020, for the Call H2020-INFRAIA-2019-1. It aims to advance the integration of national efforts in high-energy astrophysics keeping the community at the cutting edge of science and technology and ensuring that observatories are at the state of the art. Furthermore it will integrate key infrastructures for on-ground test and calibration of space-based instrumentation and promote their coordinated use. CNR provides to the AHEAD community the research infrastructures available to the ISM and IOM beamlines at the Elettra Italian National synchrotron laboratory. It contributes with the participation to the Transnational Access Activity 1 (TA1) of the research facility BABE for the characterization and diagnostics of optical elements, devices and related constituent materials (WP5, IOM-CNR), and to the Joint Research Action 5 for laboratory measurements of wavelengths and cross sections of inner-shell transitions of astrophysically abundant ions (WP13, ISM-CNR).

Implementation of in-situ and operando experimental set-ups for bridging the pressure gap in characterization techniques based on monitoring of photoelectron emission has made significant achievements at several beamlines at Elettra synchrotron facility. These set-ups are now operational and have been successfully used to address unsolved issues exploring events occurring at solid-gas, solid-liquid and solid-solid interfaces of functional materials. The sections in the article communicate the research opportunities offered by the current set-ups at APE, BACH, ESCAmicroscopy and Nanospectroscopy beamlines and outline the next steps to overcome the present limits.

The space between a metal surface and a two-dimensional cover can be regarded as a nanoreactor, where confined molecule adsorption and surface reactions may occur. In this work, we report CO intercalation and reactivity between a graphene-hexagonal boron nitride (h-BNG) heterostructure and Pt(111). By employing high resolution X-ray photoemission spectroscopy (XPS) we demonstrate the molecular intercalation of the full h-BNG overlayer and stabilization of a dense (root 19 x root 19)R234 degrees-13CO layer on Pt(111) under ultra-high vacuum at room temperature. We provide experimental evidence of a weakened CO-metal bond due to the confinement effects of the 2D cover. Temperature-programmed XPS results reveal that CO desorption is kinetically delayed and occurs at a higher temperature than on bare Pt(111). Moreover, CO partially reacts with the h-BNG layer to form boron-oxide species, which affect repeated CO intercalation. Finally, we found that the properties of the system towards interaction with CO can be considerably recovered using high temperature treatment.

Thin films of an iron(ii) complex with a photochromic diarylethene-based ligand and featuring a spin-crossover behaviour have been grown by sublimation in ultra-high vacuum on highly oriented pyrolytic graphite and spectroscopically characterized through high-resolution X-ray and ultraviolet photoemission, as well as via X-ray absorption. Temperature-dependent studies demonstrated that the thermally induced spin-crossover is preserved at a sub-monolayer (0.7 ML) coverage. Although the photochromic ligand ad hoc integrated into the complex allows the photo-switching of the spin state of the complex at room temperature both in bulk and for a thick film on highly oriented pyrolytic graphite, this photomagnetic effect is not observed in sub-monolayer deposits. Ab initio calculations justify this behaviour as the result of specific adsorbate-substrate interactions leading to the stabilization of the photoinactive form of the diarylethene ligand over photoactive one on the surface.

Two-dimensional boron-nitrogen-carbon heterostructures with variable composition and interaction strength were obtained by one-step one-precursor synthetic route based on dimethylamine borane pyrolysis by changing the metallic surfaces and the temperature of growth. Hybrid single layers composed mainly of hexagonal boron nitride and graphene domains (h-BNG) with different relative concentration and surface hybridization were grown on polycrystalline metallic foils including Pt and earth abundant metals such as Ni and Fe. An almost free-standing layer of h-BNG grown on Pt was successfully transferred on a SiO 2 /Si substrate by a simple electrolytic delamination. The atmospheric gas intercalation between h-BNG and Pt of the sample stored in air before the transfer procedure was demonstrated to be effective for a facile h-BNG detachment from the metal during the delamination bubbling process. This facile and flexible synthesis and transfer route opens up the way to applications of hybrid B-N-C monolayer in technology, catalysis and 2D confined chemistry, gas-sensing and hydrogen storage.

We have experimentally determined the lateral registry and geometric structure of free-base porphine (2H-P) and copper-metalated porphine (Cu-P) adsorbed on Cu(111), by means of energy-scanned photoelectron diffraction (PhD), and compared the experimental results to density functional theory (DFT) calculations that included van der Waals corrections within the Tkatchenko-Scheffler approach. Both 2H-P and Cu-P adsorb with their center above a surface bridge site. Consistency is obtained between the experimental and DFT-predicted structural models, with a characteristic change in the corrugation of the four N atoms of the molecule's macrocycle following metalation. Interestingly, comparison with previously published data for cobalt porphine adsorbed on the same surface evidences a distinct increase in the average height of the N atoms above the surface through the series 2H-P, Cu-P, and cobalt porphine. Such an increase strikingly anti-correlates the DFT-predicted adsorption strength, with 2H-P having the smallest adsorption height despite the weakest calculated adsorption energy. In addition, our findings suggest that for these macrocyclic compounds, substrate-to-molecule charge transfer and adsorption strength may not be univocally correlated.

In order to optimize the performance of devices based on porphyrin thin films it is of great importance to gain a physical understanding of the various factors which affect their charge transport and light-harvesting properties. In this work, we have employed a multi-technique approach to study vacuum deposited zinc octaethyl porphyrin (ZnOEP) thin films with different degrees of long-range order as model systems. An asymmetrical stretching of the skeletal carbon atoms of the porphyrin conformer has been observed and attributed to ordered molecular stacking and intermolecular interactions. For ordered films, a detailed fitting analysis of the X-ray absorption near edge structure (XANES) using the MXAN code establishes a symmetry reduction in the molecular conformer involving the skeletal carbon atoms of the porphyrin ring; this highlights the consequences of increased ?-? stacking of ZnOEP molecules adopting the triclinic structure. The observed asymmetrical stretching of the ? conjugation network of the porphyrin structure can have significant implications for charge transport and light harvesting, significantly influencing the performance of porphyrin based devices.

Gold nanoparticles (AuNPs), which are strongly hydrophilic and dimensionally suitable for drug delivery, were used in loading and release studies of two different copper(I)-based antitumor complexes, namely [Cu(PTA)4] + [BF4]- (A; PTA = 1, 3, 5-triaza-7-phosphadamantane) and [HB(pz)3Cu(PCN)] (B; HB(pz)3 = tris(pyrazolyl)borate, PCN = tris(cyanoethyl)phosphane). In the homoleptic, water-soluble compound A, the metal is tetrahedrally arranged in a cationic moiety. Compound B is instead a mixed-ligand (scorpionate/phosphane), neutral complex insoluble in water. In this work, the loading procedures and the loading efficiency of A and B complexes on the AuNPs were investigated, with the aim to improve their bioavailability and to obtain a controlled release. The non-covalent interactions of A and B with the AuNPs surface were studied by means of dynamic light scattering (DLS), UV-Vis, FT-IR and high-resolution x-ray photoelectron spectroscopy (HR-XPS) measurements. As a result, the AuNPs-A system proved to be more stable and efficient than the AuNPs-B system. In fact, for AuNPs-A the drug loading reached 90%, whereas for AuNPs-B it reached 65%. For AuNPs-A conjugated systems, a release study in water solution was performed over 4 days, showing a slow release up to 10%.

The effects of Cr on local environment and electronic structure of rutile TiO2 are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities CrTi 0 and CrTi 1- as well as Cr-oxygen vacancy complex 2CrTi + VO are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO2 at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t 2g states of the Cr ions in order to reach the stable oxidation state of Cr3+. Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO2 cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO2 are very sensitive to the concentration of Cr. © 2018 The Author(s).

High resolution photoemission with synchrotron radiation was used to study the interface formation of a thin layer of C60 on 6H-SiC(0 0 0 1)-(3 × 3), characterized by protruding Si-tetramers. The results show that C60 is chemisorbed by orbital hybridization between the highest-occupied molecular orbital (HOMO) and the p z orbital of Si adatom at the apex of the tetramers. The covalent nature of the bonding was inferred from core level as well as valence band spectra. The Si 2p spectra reveal that a large fraction (at least 45%) of the Si adatoms remain unbound despite the reactive character of the associated dangling bonds. This is consistent with a model in which each C60 is attached to the substrate through a single covalent C60-Si bond. A binding energy shift of the core levels associated with sub-surface Si or C atoms indicates a decrease of the SiC band bending caused by a charge transfer from the C60 molecules to the substrate via the formation of donor-like interface states. © 2018 IOP Publishing Ltd.

The chemical compatibility between carbon free olivine-LiNiPO4 thin films used as cathode material and LiPF6/DMC/FEC/0.2%- TMB liquid electrolyte was studied by soft-photoelectron spectroscopy, Ni L- and O K- XANES combined with electrochemical experiments. The stability of the electrolyte-electrode interface at a high charging potential strongly depends on the temperature of LiNiPO4 preparation. For the films grown at 740°C, the chemical composition of the interface is not changed even at a charging potential of 5.2 V, whereas the electrolyte-electrode interface of LiNiPO 4 grown at lower temperatures (675°C) decomposes at 5.1 V, involving the cathode material in the chemical reaction. © The Author(s) 2018.