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Unraveling structure–activity relationships is a key objective of catalysis. Unfortunately, the intrinsic complexity and structural heterogeneity of materials stand in the way of this goal, mainly because the activity measurements are area-averaged and therefore contain information coming from different surface sites. This limitation can be surpassed by the analysis of the noise in the current of electrochemical scanning tunneling microscopy (EC-STM). Herein, we apply this strategy to investigate the catalytic activity toward the hydrogen evolution reaction of monolayer films of MoSe₂. Thanks to atomically resolved potentiodynamic experiments, we can evaluate individually the catalytic activity of the MoSe₂ basal plane, selenium vacancies, and different point defects produced by the intersections of metallic twin boundaries. The activity trend deduced by EC-STM is independently confirmed by density functional theory calculations, which also indicate that, on the metallic twin boundary crossings, the hydrogen adsorption energy is almost thermoneutral. The micro- and macroscopic measurements are combined to extract the turnover frequency of different sites, obtaining for the most active ones a value of 30 s⁻¹ at −136 mV vs RHE.

The development of catalysts for the hydrogen evolution reaction is pivotal for the hydrogen economy. Thin iron films covered with monolayer graphene exhibit outstanding catalytic activity, surpassing even that of platinum, as demonstrated by a method based on evaluating the noise in the tunnelling current of electrochemical scanning tunnelling microscopy. Using this approach, we mapped with atomic-scale precision the electrochemical activity of the graphene–iron interface, and determined that single iron atoms trapped within carbon vacancies and curved graphene areas on step edges are exceptionally active. Density functional theory calculations confirmed the sequence of activity obtained experimentally. This work exemplifies the potential of electrochemical scanning tunnelling microscopy as the only technique able to determine both the atomic structure and relative catalytic performance of atomically well-defined sites in electrochemical operando conditions and provides a detailed rationale for the design of novel catalysts based on cheap and abundant metals such as iron. [Figure not available: see fulltext.].

We report the study of two-dimensional graphitic carbon nitride (GCN) functionalized with copper single atoms as a catalyst for the reduction of CO2 (CO2RR). The correct GCN structure, as well as the adsorption sites and the coordination of the Cu atoms, was carefully determined by combining experimental techniques, such as X-ray diffraction, transmission electron microscopy, X-ray absorption, and X-ray photoemission spectroscopy, with DFT theoretical calculations. The CO2RR products in KHCO3 and phosphate buffer solutions were determined by rotating ring disk electrode measurements and confirmed by 1H-NMR and gas chromatography. Formate was the only liquid product obtained in bicarbonate solution, whereas only hydrogen was obtained in phosphate solution. Finally, we demonstrated that GCN is a promising substrate able to stabilize metal atoms, since the characterization of the Cu-GCN system after the electrochemical work did not show the aggregation of the copper atoms.

We have investigated the electronic response of single crystals of indium selenide by means of angle-resolved photoemission spectroscopy, electron energy loss spectroscopy and density functional theory. The loss spectrum of indium selenide shows the direct free exciton at ~1.3 eV and several other peaks, which do not exhibit dispersion with the momentum. The joint analysis of the experimental band structure and the density of states indicates that spectral features in the loss function are strictly related to single-particle transitions. These excitations cannot be considered as fully coherent plasmons and they are damped even in the optical limit, i.e. for small momenta. The comparison of the calculated symmetry-projected density of states with electron energy loss spectra enables the assignment of the spectral features to transitions between specific electronic states. Furthermore, the effects of ambient gases on the band structure and on the loss function have been probed.

By means of a combination of surface-science spectroscopies and theory, we investigate the mechanisms ruling the catalytic role of epitaxial graphene (Gr) grown on transition-metal substrates for the production of hydrogen from water. Water decomposition at the Gr/metal interface at room temperature provides a hydrogenated Gr sheet, which is buckled and decoupled from the metal substrate. We evaluate the performance of Gr/metal interface as a hydrogen storage medium, with a storage density in the Gr sheet comparable with state-of-the-art materials (1.42 wt %). Moreover, thermal programmed reaction experiments show that molecular hydrogen can be released upon heating the water-exposed Gr/metal interface above 400 K. The Gr hydro/dehydrogenation process might be exploited for an effective and eco-friendly device to produce (and store) hydrogen from water, i.e., starting from an almost unlimited source.

Singly and multiply doped graphene oxide quantum dots have been synthesized by a simple electrochemical method using water as solvent. The obtained materials have been characterized by photoemission spectroscopy and scanning tunneling microscopy, in order to get a detailed picture of their chemical and structural properties. The electrochemical activity toward the oxygen reduction reaction of the doped graphene oxide quantum dots has been investigated by cyclic voltammetry and rotating disk electrode measurements, showing a clear decrease of the overpotential as a function of the dopant according to the sequence: N ∼ B > B,N. Moreover, assisted by density functional calculations of the Gibbs free energy associated with every electron transfer, we demonstrate that the selectivity of the reaction is controlled by the oxidation states of the dopants: as-prepared graphene oxide quantum dots follow a two-electron reduction path that leads to the formation of hydrogen peroxide, whereas after the reduction with NaBH4, the same materials favor a four-electron reduction of oxygen to water. (Chemical Equation Presented).

The conversion of anodic TiO2 films into TiOxCy in ultrahigh-vacuum (UHV) has been traced by photoemission spectroscopy in order to optimize the process parameters and study the different phase stabilities. In addition, density functional theory (DFT) calculations have been performed in order to elucidate the main questions about TiOxCy composition and stability. The experimental data indicate that the anodic TiO2 film is stable both in UHV and ethylene background up to ca. 600 K, and at this temperature, it starts to reduce leading to suboxide TiOx species. Above ca. 750 K, the formation of TiOxCy starts, since the oxygen vacancies begin to be replaced by carbon atoms. A surface enrichment in TiO2 and elemental carbon has been detected on the converted TiOxCy film at room temperature. Real-time measurements have shown that this phenomenon takes place during the cool down process and DFT calculations suggest a possible explanation: as the temperature decreases below ca. 750 K (temperature at which the formation of TiOxCy starts), the TiOxCy phase is not thermodynamically stable, and it decomposes into TiO2 and elemental carbon. The comparison of the experimental valence band data with DFT results has also allowed to establish that the film surface is not homogeneous and that segregation of TiO and TiC systems may take place. On the other hand, the local compositional study carried out by scanning photoelectron microscopy has shown that the conversion of the film is not homogeneous but depends on the grain orientation, in particular crystallites with an orientation close to <21 ̄1 ̄0> and <101 ̄0> planes show a higher grade of conversion. Both experimental and DFT data validate the use of TiOxCy as an innovative support for electrocatalysis.

We demonstrate that graphene oxide can be efficiently reduced by evaporating metal Titanium in high vacuum. A detailed description of this reaction is provided by combining in situ photoemission spectroscopy measurements and DFT calculations: the titanium atoms readily react with the oxygenated groups of graphene oxide, disrupting the C–O bonds, with the consequent formation of titania and the recovery of the sp2 hybridized carbon atoms. When all surface oxygen is consumed, titanium can react with the carbon substrate and form carbidic species. Resonant photoemission spectroscopy measurements allow identifying the presence and exact energy position in the valence band of the Ti–C and Ti–O–C states, which are supposed to control the electron and energy transfer across the TiO2/ graphene interface. Therefore with this study we provide a versatile method and the rationale for controlling, at the atomic level, the nature of the interface of graphene/metal oxide nanocomposites.

The emerging fields of graphene-based magnetic and spintronic devices require a deep understanding of the interface between graphene and ferromagnetic metals. This work reports a detailed investigation at the nanometer level of the Fe-graphene interface carried out by angle-resolved photoemission, high-resolution photoemission from core levels, and scanning tunnelling microscopy. Quasi-freestanding graphene was grown on Pt(111), and the iron film was either deposited atop or intercalated beneath graphene. Calculations and experimental results show that iron strongly modifies the graphene band structure and lifts its pi band spin degeneracy.

The structure of a rectangular TiO2 nanophase grown epitaxially on a Pt(111) substrate has been investigated by a combined experimental-theoretical approach. It is found that such nanophase is stoichiometric, incommensurate to the substrate and has the structure of a lepidocrocite layer. The film is weakly bound to the metal surface via the O atoms of the oxide layer and consequently it does not have a fully wetting behavior. Two almost iso-energetic structures have been found based on first principles DFT calculations, one characterized by a short and one by a long interface distance, this latter being energetically slightly preferred. However, when the strain due to lattice mismatch is accommodated on the Pt(111) substrate instead of the TiO2 film, only the long interface structure is found. The analysis of measured and computed valence band spectra and STM images supports the long interface, weakly interacting model. (C) 2007 Elsevier B.V. All rights reserved