An electrifying view on catalysis

The future of chemistry is ‘electrifying’: With increasing availability of cheap electrical energy from renewables, it will soon become possible to drive many chemical processes by electrical power. In this way, chemical products and fuels can be produced via sustainable routes, replacing current processes which are based on fossil fuels.

In most cases, such electrically driven reactions make use of so-called electrocatalysts, complex materials which are assembled from a large number of chemical componentAs. The electrocatalyst plays an essential role: It helps to run the chemical reaction while keeping the loss of energy minimal, thereby saving as much renewable energy as possible. In most cases, electrocatalysts are developed empirically and the chemical reactions at their interfaces are poorly understood. A better understanding of these processes is essential, however, for fast development of new electrocatalysts and for a directed improvement of their lifetime, one of the most important factors that currently limit their applicability.

>Read more on the Elettra website

Figure:  Introducing well-defined model electrocatalysts into the field of electrochemistry.

Megachirella -the mother of all lizards

A new international research rewrites the history of reptiles starting from a fossil found in the Dolomites.

The origin of lizards and snakes should be pushed back by about 75 million years, as documented by a small reptile, Megachirella wachtleri, found almost 20 years ago in the Dolomites and rediscovered today thanks to cutting-edge techniques in the field of 3D analysis and the reconstruction of evolutionary relationships. Evidence to this effect has been provided by an international paleontological research with the participation of the MUSE Science Museum of Trento, in collaboration with the “Abdus Salam” International Centre of Theoretical Physics of Trieste, the Enrico Fermi Centre of Rome and Elettra Sincrotrone Trieste. The results have been published in the prestigious science journal Nature, which has also dedicated its cover image to research.

The international team has identified Megachirella wachtleri – a small reptile which lived approximately 240 million years ago in what are today the Dolomites – the most ancient lizard in the world thereby providing key insight into the evolution of modern lizards and snakes.
The data – obtained by 3D X-ray imaging techniques and the analysis of DNA sequences – suggest that the origin of “squamates”, i.e. the group comprising lizards and snakes,is older than previously thought and that it can be dated to approximately 250 million years ago, before the most extensive mass extinction in history.

>Read more on the Elettra Sincrotrone Trieste website
>Watch here a video about the scientific discovery

Image: Megachirellawandering amidst the lush vegetation that approximately 240 million years ago surrounded the dolomitic beaches.
Credit: Davide Bonadonna

 

Tailoring the surface chemical reactivity of transition‐metal dichalcogenide PtTe2 crystals

Recently, the PtX2 (X=S, Se, Te) class of transition-metal dichalcogenides has emerged as one of the most promising among layered materials “beyond graphene” for the presence of high room-temperature electron mobility and, moreover, bulk type-II Dirac fermions, arising from a tilted Dirac cone.
Information on the ambient stability of PtTe2 is a crucial step in order to evaluate the feasibility of its exploitation in technology. Moreover, the possibility to tune surface chemical reactivity by appropriate surface modification is an essential step for its employment for diverse applications, especially in catalysis.
By means of experiments with several surface-science spectroscopies and density functional theory, an international team of researchers from Italy, Republic of Korea, and Taiwan (coordinated by Graphene Labs of Istituto Italiano di Tecnologia) has investigated the reactivity of the PtTe2 surface toward most common ambient gases (oxygen and water), under the framework of the European Graphene Flagship-Core1 project.
To assess the surface chemical reactivity of PtTe2, X-ray photoelectron spectroscopy (XPS) carried out at the APE-HE beamline has been combined with high-resolution electron energy loss (HREELS) experiments and with density functional theory.
From the analysis of Te 3d core-level spectra in XPS and from the featureless vibrational spectrum in HREELS, it has been demonstrated that as-cleaved defect-free PtTe2 surface is inert toward most common ambient gases (oxygen and water).
In the evaluation of the ambient stability of PtTe2, the possible influence of Te vacancies on surface chemical reactivity deserves particular attention. As a matter of fact, Te vacancies may appear on non-stoichiometric samples during the growth process. To check the influence of Te vacancies on ambient stability of PtTe2, Te vacancies have been intentionally introduced in stoichiometric PtTe2 samples by Ar-ion sputtering. After exposing to O2 the PtTe2 surface defected by ion sputtering, with a Pt:Te ratio of 39:61, spectral features related to Te(IV) species appear, arising from the formation of Te=O bonds in a tellurium-oxide phase. The Te(IV) components are the most intense lines in the Te 3d XPS spectra for the case of air-exposed defected samples (see Figure 1). Concerning reactivity to water, it adsorbs molecularly even at room temperature on defected PtTe2. These findings also imply that the presence of Te vacancies is able to jeopardize the ambient stability of uncapped PtTe2-based devices, with a subsequent necessity to reduce the amount of Te vacancies for a successful technological exploitation of PtTe2.

>Read more on the Elettra website

Figure: XPS spectra of Te-3d core levels acquired for: defected PtTe2 (green curve), the same surface exposed to 106 L of O2 (black curve) and air-exposed defected PtTe2 (yellow curve). The photon energy is 745 eV. 

LEAPS and FELs of Europe meetings at Elettra

On March 12-13 Elettra-Sincrotrone Trieste hosted the 2nd meeting of General Assembly (GA) of the League of European Accelerator-based Photon Sources (LEAPS), a strategic consortium that includes 16 Synchrotron Radiation and Free Electron Laser (FEL) user facilities in Europe based in 10 different European countries .
This followed the LEAPS Launch Event in Brussels on November 13, 2017. The main topics of the GA meeting were the LEAPS Governance Structure and the LEAPS Strategy Paper to be forwarded to the EU Commission during the Bulgarian Presidency Conference on Research Infrastructures in Sofia, 22-23 March.

>Read more on the Elettra and FERMI website

Image: LEAPS General Assembly and Coordination Board group picture.
Credit: Fotorolli

Functionalized graphdiyne nanowires

… on-surface synthesis and assessment of band structure, flexibility, and information storage potential

With their extraordinary mechanical and electronic properties carbon-based nanomaterials are central in 21st century research and carry high hopes for future nanotechnology applications. Established sp2-hybridized scaffolds include carbon nanotubes (CNTs), graphene sheets, and graphene nanoribbons. Recently, the interest in carbon allotropes incorporating both sp2and sp-hybridized atoms rose tremendously, especially for the most popular member, the so-called graphdiyne. According to theory, the related nanomaterials possess characteristics desirable for applications such as molecular electronics, energy storage, gas filtering and light harvesting. However, achieving the targeted materials with high quality remained challenging until now.
Here, we employed covalent on-surface synthesis on well-defined metal substrates under ultra-high vacuum (UHV) conditions to the homocoupling reaction of terminal alkyne compounds and fabricated the first functionalized graphdiyne (f-GDY) nanowires. Combining the substrate templating of the Ag(455) vicinal surface with specifically designed CN-functionalized precursors we achieved the controlled polymerization to atom-precise strands with their length reaching 40 nm. The left panel of Figure 1a depicts a scanning tunneling microscopy (STM) image of an area of the silver surface featuring two step edges where an example of such a f-GDY wire is lying at the lower side of the right step edge. The right panel displays a molecular model of the situation highlighting the structure of the nanowire adsorbed in the lower terrace (darker blue) consisting of covalently coupled monomers (red outline) with the CN moieties pointing towards the atoms of the upper terrace (brighter blue).

>Read more on the Elettra Sincrotrone website

Figure: (extract)  Synthesis and characterization of functionalized graphdiyne nanowires. a) STM topograph of a f-GDY polymer covering the left step edge. b) ARPES data: Before annealing a non-dispersing feature originates from the HOMO of the monomer. After annealing a dispersing features (blue) can be identified. c) Schematic representation of the deduced intrinsic band structure of the f-GDY nanowires. d) STM topograph of a strongly bent nanowire. e) Information storage thru conformational cis-trans switching of benzonitrile units. Full image here.

Research on the teeth of a prehistoric fetus

It gives us information about the last months of a mother and child, who lived 27.000 years BP.

Fossil records enable a detailed reconstruction of our planet’s history and of the evolution of our species. Dental enamel is a sort of biological archive that constantly tracks periods of good and bad health, while forming. Prenatal enamel, which grows during intrauterine life, reports the mother’s history as well.

We have studied fossil records found in the “Ostuni 1” burial site, discovered in Santa Maria di Agnano in Puglia in 1991 by Donato Coppola (Università di Bari, Italy) and dated back over 27,000 years. More specifically, we were interested in the teeth of a fetus found in the pelvic area of the skeleton of a young girl. By analysing the still forming teeth of the baby, it has been possible to obtain information about the health condition of the mother during the last months of pregnancy, to establish the gestational age of the fetus, and also to identify some specificities of the embryonal development. For the first time, it has been possible to reconstruct life and death of an ancient fetus and, at the same time, to shed light on its mother’s health.

Three still-forming incisors, belonging to the fetus, have been visualized and analyzed by means of X-ray microtomography at Elettra. The preliminary analysis on a portion of the fetal mandible, realized at the TomoLab laboratory allowed us to study the still-forming incisor contained within it (see Fig. 1). Thanks to the unique properties of synchrotron radiation and using a specifically-developed methodology, a high resolution 3D analysis has been carried out on the teeth at the SYRMEP beamline. This approach, allowed us to carry out a virtual histological analysis of the precious fossil teeth, revealing the finest structures of the dental enamel in a non-destructive way.

>Read more on the Elettra website

Image:  Pseudo color rendering of the virtual histological section of the Ostuni1b’s upper left deciduous central incisor. The corresponding CT scan has been acquired at the SYRMEP beamline in phase-contras mode.

Apply for the Kai Siegbahn prize 2018

The Prize was established in 2009 in honour of Kai Siegbahn, founder of Nuclear Instruments and Methods A (NIMA), who had a strong and lasting commitment to advancing synchrotron radiation science.

The Editorial Board of NIMA is currently accepting nominations for the 2018 award, and we are counting on you to help us identify potential honorees! We invite you to review the award criteria, and to nominate a worthy colleague.

All nominations should be submitted to the Committee Chair by March 31 2018:

Prof. Fulvio Parmigiani, Kai Siegbahn Chair
Department of Physics, University of Trieste
International Faculty, University of Cologne,
Elettra Sincrotrone Trieste S.C.p.A.
Email: fulvio.parmigiani@elettra.trieste.it

Nomination criteria:

The Prize aims to recognize and encourage outstanding experimental achievements in synchrotron radiation research with a significant component of instrument development. Particular preference will be given to the development of synchrotron radiation spectroscopies.

Rules and eligibility:

Nominations are open to scientists of all nationalities without regard to the geographical site at which the work was performed. Usually, the prize shall be awarded to one person but it may be shared if all recipients have contributed to the same accomplishment. The prize recipient should be 45 years old or younger at the time of selection.

Nominations are accepted from the NIMA advisory board, the NIMA board of editors, synchrotron radiation facility directors as well as from scientists engaged in synchrotron radiation science. Nomination packages should include a nominating letter, at least one supporting letter, a list of five papers on which the award is based as well as a proposed citation for the award.

Enhanced magnetic hybridization of a spinterface

Interfaces between organic semiconductors and ferromagnetic metals offer intriguing opportunities in the rapidly developing field of organic spintronics. Understanding and controlling the spin-polarized electronic states at the interface is the key toward a reliable exploitation of this kind of systems. It is indeed important to master and reliably reproduce the chemical reactions responsible of the spin-polarization at the interface.

Here we propose an approach consisting in the insertion of an ultrathin, two-dimensional Cr4O5 magnetic oxide layer at the interface between a C60 fullerene organic semiconductor and a Fe(001) ferromagnetic metal to both maximize the spin polarization and to overcome the reproducibility issues usually present in case of direct interface between metallic layer and organic semiconductor.
C60 fullerene showed a greater surface diffusivity when growing on Cr4O5 compared to the Fe(001) case. From the first stages of surface coverage, C60 tends to form islands rather than isolated molecules, leading to a well-ordered growth at higher thicknesses (Figure 1, above).

>Read more on the Elettra website

Figure 1STM image 200 x 200 nm2 of the surface of a C60/ Cr4O5/Fe(001) sample with a fullerene coverage of about 0.5 ML. The image was taken at room temperature with ΔV= 1.7 V, I = 400 pA.

Subfilamentary Networks in Memristive Devices

Redox-based memristive devices are one of the most attractive emerging memory technologies.

…in terms of scaling, power consumption and speed. In these devices, external electrical stimuli cause changes of the resistance of an oxide layer sandwiched between two metal electrodes. In the simplest application, the device can be set into a low resistance state (LRS) and reset into a high resistance state (HRS), which may encode a logical one and zero, respectively. The major obstacle delaying large-scale application, however, is the large cycle-to-cycle (C2C) and device-to-device (D2D) variability of both LRS and HRS resistance values. These variabilities describe the stochastic nature of the switching process within one cell, resulting in different resistances obtained for each switching cycle and different resistances obtained for different cells on the same chip.

Read more on the Elettra website.

Image:(a) Schematic of the device geometry. A SrTiO3 layer (blue) is sandwiched between a Nb:SrTiO3 bottom electrode (dark grey) and graphene top electrode (grey honeycomb lattice). The graphene electrode is contacted through a metal lead, which is electrically separated from the continuous bottom electrode, allowing for biasing inside PEEM instruments. (b) Quasistatic I-V curve of a representative graphene/SrTiO3/Nb:SrTiO3 device. The bottom electrode serves as virtual ground, while the bias is applied to the graphene top electrode. (c) PEEM image of a graphene/Al2O3/SrTiO3 device in the LRS at an electron energy E – EF of 3.4 eV. Scale bar, 5 µm. (d) PEEM image of the same device after Reset. (e) and (f) PEEM images after one additional Set and Reset operation, respectively. Insets: magnified photoemission threshold map of the area around the conductive filament. The maps were obtained by fitting the threshold spectrum for each pixel.

Topological insulator gap in graphene contacted with Pb

Up to now the proposed modifications do not allow to introduce graphene to existing electronic devices.

Graphene is the most promising two dimensional material for nanoelectronic applications featuring the relativistic-like electronic spectrum. Contact of graphene with various materials and its functionalization allows to manipulate the electronic structure, e.g. to change the conductivity type and band gap creation. The latter is of great interest due to the requirements for graphene transistor realisation. Furthermore, graphene contact with heavy/magnetic metals results in the lifting of the spin degeneracy of the Dirac cone, opening the spintronics field for its applications. However, up to now the proposed modifications do not allow to introduce graphene to existing electronic devices.

>Read more on the Elettra website.

Image: a) Sketch of the studied system, the Pb atoms presented by yellow spheres; b) ARPES image of graphene/Pb/Pt(111) in the region of K point, taken as a sum of two spectra with p-and s-polarization of light; c) schematic spin structure of the graphene states in the case of large “intrinsic” spin-orbit interaction d) ARPES mapping of the system in two orthogonal k-directions near the K point of graphene.

Multi-orbital charge transfer at highly oriented organic/metal interfaces

Organic-based device performances have been rapidly improving in the last years, making them suitable for large-scale industrial applications, involving photo-voltaic cells, light emission systems and building of larger flexible electronics. In parallel, basic research has intensively been focused on the chemical and physical properties of semiconducting π-conjugated organic molecules, as they appear to be promising for organic-based device construction. In particular, in controlling the charge injection on such devices, a predominant role is played by the molecule-substrate interaction. Charge transfer at the molecule-metal interface strongly affects the overall physical and magnetic properties of the system, and ultimately, the device performance.
Read more on the Elettra website.

Image: (a) STM image including two Ni-TPP domains, labeled with A and B, respectively. STM image parameters: Vb = −1.5 V, It = 0.2 nA, image size 15 × 20 nm2, measured at 4.3 K. (b) . Proposed adsorption model for Ni-TPP/Cu(100), side view. (c) Valence band photoemission spectra of clean Cu(100) and Ni-TPP/Cu(100) acquired at 26 eV photon energy. (d) PDOS onto molecular orbitals for the Ni-TPP/Cu(100) system. The energy position of the corresponding gas-phase molecular orbitals, aligned with respect to the vacuum level, is indicated with colored bars on the top axis. (e) Comparison between μ-ARPES measured patterns (left) and the correspondent calculated |FT|2 of the molecular orbitals (right).

Ubiquitous formation of type-I and type-II bulk Dirac cones

… and topological surface states from a single orbital manifold in transition-metal dichalcogenides

Transition-metal dichalcogenides (TMDs) are renowned for their rich and varied properties. They range from metals and superconductorsto strongly spin-orbit-coupled semiconductors and charge-density-wave systems with their single-layer variants one of the most prominent current examples of two-dimensional materials beyond graphene.Their varied ground states largely depend on the transition metal d-electron-derived electronic states, on which the vast majority of attention has been concentrated to date.

>Read more on the Elettra website.

Image: Chalcogen-derived topological ladder in PdTe2.(a) Orbitally-resolved bulk electronic structure of PdTe2, indicating dominantly chalcogen-derived orbital character for the states in the vicinity of the Fermi level. (b) The measured out-of-plane dispersion together with the calculated band structure. Measured (c) and calculated (d) in-plane dispersion. (e,f) Spin-resolved energy distribution curves along the lines shown in (c).

Quantum spectroscopy, for the measurements of dynamical current current thermalization

Nearly all spectroscopic measurements deals with the measurements of the average properties of the material. As an example, the reflectivity of a material is simply defined by the ratio between the number of photons which are reflected by the sample divided by the number of those arriving on it. The interest in measuring mostly average properties is the main drive of the standard scientific practice of repeating the measurements a lot of times so that the error made in one single measurements is averaged out by the repetition of the measurements. In this context the noise which determines fluctuation of the repeated measurements have always been considered as an impediment to a good quality measurements which needs to be mitigated by careful experimentalists.
The approach of repeated measurements is employed conspicuously in pump-probe experiments which are the prime way to study condensed matter out of its equilibrium state. In standards optical pump-probe experiments, ultrashort pulses are always used in pairs. The pump triggers the dynamical response and the probe is used to detect changes in the optical properties of the sample.

Read more on the Elettra website.

Image: Schematic view of the pump-probe set-up used for the experiments. The intensity of every single probe pulse was separately acquired with low-electronic-noise detectors for every pump-probe delay.

Maximal Rashba-like spin splitting via kinetic-energy-coupled inversion-symmetry breaking

Research collaboration led by Professor Philip King from University of St. Andrews, and comprising the researchers from Max Planck Institute for Chemical Physics of Solids in Dresden, Institute for Theoretical Physics of the University of Heidelberg and researchers from I05 beamline at Diamond Light Source and APE beamline at Elettra, described a new route to maximise the spin-splitting of surface states.
The electronic properties of surfaces are often different from those of the bulk. In particular, the intrinsically broken symmetries of the surface compared with the bulk of the material allow for appearance of the new electronic surface states. For the systems in which spin-orbit interaction is strong, a non-negligible separation of these states according to their spin takes place. The spin splitting of surface- or interface-localized two-dimensional electron gases is characterized by a locking of the electron spin perpendicular to its momentum.

Read more on the Elettra website.

(a) Bulk and surface Fermi surfaces of PtCoO2 measured by ARPES; (b) Expected spin texture of the surface states; (c) Spin-resolved ARPES measurements of an in-plane spin polarization (〈Sy〉) of the Fermi surface for the cut along kx.

Fluorination of suspended graphene

Functionalization is a well-established method to manipulate the electronic properties of graphenes

It consists in the substitution of carbon atoms in the hexagonal network by other elements such as heteroatoms (nitrogen or boron, the most common) or in the introduction of more complex functional groups.

The customization of the graphene exceptional electronic properties by the functionalization opens different avenues for future applications including bio and chemical-sensors. Among various functionalization methods, plasma process and ion irradiation have been widely employed for the modification of surface chemical composition and properties. These techniques have attracted the attention of a vast scientific audience because they can be used to tailor the surface reactivity in different materials making them suitable for various applications ranging from chemical sensing to medical implants. In particular, the fluorination of graphene allows the tuning of the optical bandgap, introducing a progressive semiconducting behaviour for increasing fluorine content ending in insulating properties for fully fluorinated graphene.

>Read More

Liquid-phase chemistry: Graphene nanobubbles

X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Absorption Spectroscopy (XAS) provide unique knowledge on the electronic structure and chemical properties of materials.

Unfortunately this information is scarce when investigating solid/liquid interfaces, chemical or photochemical reactions in ambient conditions because of the short electron inelastic mean free path (IMFP) that requires a vacuum environment, which poses serious limitation on the application of XPS and XAS to samples operating in atmosphere or in the presence of a solvent. One promising approach to enable the use of conventional electron spectroscopies is the use of thin membrane, such as graphene (Gr), which is transparent to both X-ray photons and photoelectrons. For these purposes, this work proposes an innovative system based on sealed Gr nanobubbles (GNBs) on a titanium dioxide TiO2 (100) rutile single crystal filled with the solution of interest during the fabrication stage (Figure 1a).

The formation of irregularly shaped vesicles with an average height of 6 nm and lateral size of a few hundreds of nanometers was proved by using a multi-technique approach involving Atomic Force Microscopy (AFM, see Figure 1b,c,d), Raman (Figure 1e) and synchrotron radiation spectroscopies (Figure 2), which have unequivocally demonstrated the presence of water inside the GNBs and the transition to a flat Gr layer after water evaporation by thermal heating up to 350 °C in ultra high vacuum (UHV).

>Read More