Fast X-ray Photoelectron Spectroscopy Research Articles

Unraveling oxygen-driven surface segregation dynamics in platinum-gold alloys

In this study we use high-energy resolution and fast X-ray Photoelectron Spectroscopy (XPS) measurements combined with Density Functional Theory (DFT) calculations to investigate the interplay between surface segregation and bulk migration of Pt atoms on Au(111) in an oxygen environment. We demonstrate that the segregation of Pt atoms is significantly influenced by the oxygen partial pressure and identify a range of O2 pressure where PtAu surface alloy formation is inhibited while promoting the formation of Au oxide. These findings are essential to understand the compositional changes in the bimetallic surface alloy, which could potentially lead to modifying the catalytic properties of PtAu up to catalyst deactivation. Our results offer a strategy to control Pt surface coverage on Au(111), a quantity that is of paramount relevance given the applications of PtAu alloys as catalysts in reactions such as the oxygen reduction reaction or the oxidation of methanol and carbon monoxide. Additionally, our findings indicate a method for controlling the composition and properties of the surface of PtAu catalysts through adjustments made during the formation of the PtAu alloy.

Growth and structure of singly oriented single-layer tungsten disulfide on Au(111)

We present a complete characterisation at the nanoscale of the growth and structure of single-layer tungsten disulfide (WS$_2$) epitaxially grown on Au(111). Following the growth process in real time with fast x-ray photoelectron spectroscopy, we obtain a singly-oriented layer by choosing the proper W evaporation rate and substrate temperature during the growth. Information about the morphology, size and layer stacking of the WS$_2$ layer were achieved by employing x-ray photoelectron diffraction and low-energy electron microscopy. The strong spin splitting in the valence band of WS$_2$ coupled with the single-orientation character of the layer make this material the ideal candidate for the exploitation of the spin and valley degrees of freedom.

Photoemission investigation of oxygen intercalated epitaxial graphene on Ru(0001)

We study the formation of epitaxial graphene on Ru(0001) using fast x-ray photoelectron spectroscopy during the growth process. The assignment of different C 1s and Ru 3d core level components and their evolution during the growth process gives a detailed insight into the graphene formation and the strongly varying graphene-Ru interaction strength within the large moiré unit cell. Subsequent intercalation of oxygen can be achieved at elevated temperature and the core level spectra show a conversion of the strongly corrugated to quasi free-standing graphene, characterised by a single narrow C 1s component. This conversion and the accompanying flattening of the graphene layer is also confirmed by x-ray photoelectron diffraction. The effect of oxygen intercalation on the electronic structure is studied using angle-resolved photoemission of the valence band states. For graphene/Ru(0001), the strong graphene-substrate hybridisation disrupts the π-band dispersion but oxygen intercalation fully restores the π-band with a strong p-doping that shifts the Dirac point 785 meV above the Fermi level. The doping of the system is highly tunable, as the additional exposure to rubidium can convert the carrier filling to n-type with the Dirac point 970 meV below the Fermi level.

On-Surface Growth Dynamics of Graphene Nanoribbons: The Role of Halogen Functionalization.

On-surface synthesis is a powerful route toward the fabrication of specific graphene-like nanostructures confined in two dimensions. This strategy has been successfully applied to the growth of graphene nanoribbons of diverse width and edge morphology. Here, we investigate the mechanisms driving the growth of 9-atom wide armchair graphene nanoribbons by using scanning tunneling microscopy, fast X-ray photoelectron spectroscopy, and temperature-programmed desorption techniques. Particular attention is given to the role of halogen functionalization (Br or I) of the molecular precursors. We show that the use of iodine-containing monomers fosters the growth of longer graphene nanoribbons (average length of 45 nm) due to a larger separation of the polymerization and cyclodehydrogenation temperatures. Detailed insight into the growth process is obtained by analysis of kinetic curves extracted from the fast X-ray photoelectron spectroscopy data. Our study provides fundamental details of relevance to the production of future electronic devices and highlights the importance of not only the rational design of molecular precursors but also the most suitable reaction pathways to achieve the desired final structures.

Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization.

Surface-confined polymerization via Ullmann coupling is a promising route to create one- and two-dimensional covalent π-conjugated structures, including the bottom-up growth of graphene nanoribbons. Understanding the mechanism of the Ullmann reaction is necessary to provide a platform for rationally controlling the formation of these materials. We use fast X-ray photoelectron spectroscopy (XPS) in kinetic measurements of epitaxial surface polymerization of 1,4-dibromobenzene on Cu(110) and devise a kinetic model based on mean field rate equations, involving a transient state. This state is observed in the energy landscapes calculated by nudged elastic band (NEB) within density functional theory (DFT), which assumes as initial and final geometries of the organometallic and polymeric structures those observed by scanning tunneling microscopy (STM). The kinetic model accounts for all the salient features observed in the experimental curves extracted from the fast-XPS measurements and enables an enhanced understanding of the polymerization process, which is found to follow a nucleation-and-growth behavior preceded by the formation of a transient state.

An Ordered Mixed Oxide Monolayer Formed by Iron Segregation on Rutile-TiO2(011): Structural Determination by X-ray Photoelectron Diffraction

Iron impurities in the rutile-TiO2(011) surface can result in the formation of an ordered, ternary iron–titanium oxide monolayer. Here the FeTi2O5 mixed oxide monolayer predicted by DFT simulations is confirmed by synchrotron based angle scanned X-ray photoelectron diffraction (XPD) studies. The ternary oxide monolayer has been synthesized on rutile-TiO2(011) substrate via two different experimental pathways: first, by segregation of Fe impurities from the bulk by annealing a clean TiO2(011) substrate in 1 × 10–7 mbar of oxygen at ∼450 °C and, second, by physical vapor deposition of Fe on clean TiO2(011) in 1 × 10–7 mbar of oxygen at ∼450 °C. For both preparation procedures an intermixed surface oxide is formed with Fe and Ti in 2+ and 4+ charge states, respectively. The surface is characterized by high-resolution and fast X-ray photoelectron spectroscopy (XPS), XPD, and low energy electron diffraction (LEED). Multiple electron scattering simulations implemented in the electron diffraction in atomic clusters (EDAC) package were performed for comparing experimental XPD patterns with structural models. The reliability of the approach was tested on XPD pattern of reconstructed clean TiO2(011)-2 × 1 surface, for which a structural model exists. The XPD pattern of the monolayer ternary iron titanium oxide is compared to structural models proposed by density functional theory (DFT)-based models.

Ultrafast x-ray photoelectron spectroscopy in the microsecond time domain

We introduce a new approach for ultrafast in situ high-resolution X-ray photoelectron spectroscopy (XPS) to study surface processes and reaction kinetics on the microsecond timescale. The main idea is to follow the intensity at a fixed binding energy using a commercial 7 channeltron electron analyzer with a modified signal processing setup. This concept allows for flexible switching between measuring conventional XP spectra and ultrafast XPS. The experimental modifications are described in detail. As an example, we present measurements for the adsorption and desorption of CO on Pt(111), performed at the synchrotron radiation facility BESSY II, with a time resolution of 500 μs. Due to the ultrafast measurements, we are able to follow adsorption and desorption in situ at pressures of 2 × 10(-6) mbar and temperatures up to 500 K. The data are consistently analyzed using a simple model in line with data obtained with conventional fast XPS at temperatures below 460 K. Technically, our new approach allows measurement on even shorter timescales, down to 20 μs.

Controlling Hydrogenation of Graphene on Ir(111)

Combined fast X-ray photoelectron spectroscopy and density functional theory calculations reveal the presence of two types of hydrogen adsorbate structures at the graphene/Ir(111) interface, namely, graphane-like islands and hydrogen dimer structures. While the former give rise to a periodic pattern, dimers tend to destroy the periodicity. Our data reveal distinctive growth rates and stability of both types of structures, thereby allowing one to obtain well-defined patterns of hydrogen clusters. The ability to control and manipulate the formation and size of hydrogen structures on graphene facilitates tailoring of its properties for a wide range of applications by means of covalent functionalization.

High-resolution fast X-ray photoelectron spectroscopy study of ethylene interaction with Ir(1 1 1): From chemisorption to dissociation and graphene formation

High-energy resolution fast X-ray photoelectron spectroscopy was used to study the thermal evolution of ethylene on Ir(1 1 1). Temperature programmed photoemission spectra of the C 1 s and Ir 4 f 7/2 core levels were measured in 400 ms/spectrum while ramping the temperature from 170 to 1120 K. The C 1 s spectra display a large variety of components, assigned to different carbon containing species present on the surface at increasing temperature, namely ethylene, ethylidene, ethylidyne, ethynyl, adsorbed carbon and finally graphene. Components due to the C–H stretch vibration excitation are clearly resolved for C 2H 4, CHCH 3 and C 2H 3. The C 1 s spectra of the last two species display also shifted components that belong to non-equivalent carbon atoms. At temperatures higher than 900 K the narrowing of C 1 s spectra is caused by graphene formation. Also the Ir 4 f 7/2 spectra are strongly affected by the presence of the different species. The clean surface component moves initially towards the bulk peak and shifts back and forth along the series, to recover the binding energy position corresponding to the clean surface when the graphene layer is completely formed. A comparison of ethylene interaction with Ir(1 1 1) and Pt(1 1 1) is presented.

放射光 X 線分光で見る白金族表面上での化学反応

A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111) and H2O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions.

Mechanism of CO oxidation reaction on O-covered Pd(111) surfaces studied with fast x-ray photoelectron spectroscopy: Change of reaction path accompanying phase transition of O domains

We studied the mechanism of CO oxidation on O-precovered Pd(111) surfaces by means of fast x-ray photoelectron spectroscopy (XPS). The oxygen overlayer is compressed upon CO coadsorption from a p(2 x 2) structure into a (square root(3) x square root(3))R30 degrees structure and then into a p(2 x 1) structure with increasing CO coverage. These three O phases exhibit distinctly different reactivities. (1) The p(2 x 2) phase does not react with CO unless the surface temperature is sufficiently high (<290 K). (2) In the square root(3) x square root(3))R30 degrees phase, the reaction occurs exclusively at island peripheries. CO molecules in a high-density phase formed under CO exposure react with oxygen atoms, leading to quite a small apparent activation energy. (3) The reaction proceeds uniformly over the islands in the p(2 x 1) phase.

Sulfate-Enhanced Catalytic Destruction of 1,1,1-Trichlorethane over Pt(111)

The catalytic destruction of 1,1,1-trichloroethane (TCA) over model sulfated Pt(111) surfaces has been investigated by fast X-ray photoelectron spectroscopy and mass spectrometry. TCA adsorbs molecularly over SO4 precovered Pt(111) at 100 K, with a saturation coverage of 0.4 monolayer (ML) comparable to that on the bare surface. Surface crowding perturbs both TCA and SO4 species within the mixed adlayer, evidenced by strong, coverage-dependent C 1s and Cl and S 2p core-level shifts. TCA undergoes complete dechlorination above 170 K, accompanied by C-C bond cleavage to form surface CH3, CO, and Cl moieties. These in turn react between 170 and 350 K to evolve gaseous CO2, C2H6, and H2O. Subsequent CH3 dehydrogenation and combustion occurs between 350 and 450 K, again liberating CO2 and water. Combustion is accompanied by SO4 reduction, with the coincident evolution of gas phase SO2 and CO2 suggesting the formation of a CO-SOx surface complex. Reactively formed HCl desorbs in a single state at 400 K. Only trace (<0.06 ML) residual atomic carbon and chlorine remain on the surface by 500 K.

N H 3 adsorption and decomposition on Ir(110): A combined temperature programmed desorption and high resolution fast x-ray photoelectron spectroscopy study

The adsorption and decomposition of NH3 on Ir(110) has been studied in the temperature range from 80 K to 700 K. By using high-energy resolution x-ray photoelectron spectroscopy it is possible to distinguish chemically different surface species. At low temperature a NH3 multilayer, which desorbs at approximately 110 K, was observed. The second layer of NH3 molecules desorbs around 140 K, in a separate desorption peak. Chemisorbed NH3 desorbs in steps from the surface and several desorption peaks are observed between 200 and 400 K. A part of the NH3ad decomposes into NH(ad) between 225 and 300 K. NH(ad) decomposes into N(ad) between 400 K and 500 K and the hydrogen released in this process immediately desorbs. N2 desorption takes place between 500 and 700 K via N(ad) combination. The steady state decomposition reaction of NH3 starts at 500 K. The maximum reaction rate is observed between 540 K and 610 K. A model is presented to explain the occurrence of a maximum in the reaction rate. Hydrogenation of N(ad) below 400 K results in NH(ad). No NH2ad or NH3ad/NH3 were observed. The hydrogenation of NH(ad) only takes place above 400 K. On the basis of the experimental findings an energy scheme is presented to account for the observations.

Direct Observation of Extremely Low Temperature Catalytic Dehydrochlorination of 1,1,1-Trichloroethane over Platinum

Fast X-ray photoelectron spectroscopy reveals that the efficient catalytic destruction of 1,1,1-trichloroethane occurs over Pt{111} surfaces at temperatures as low as 150 K. Decomposition occurs via rapid, sequential C-Cl bond scission to form an alkylidyne surface intermediate that in turn dehydrogenates above room temperature. Atomic chlorine liberated during dehydrochlorination undergoes efficient reaction with surface hydrogen, resulting in the evolution of gaseous HCl and small amounts of ethane, presumably via ethylidyne hydrogenation. Irreversible dehydrogenation of residual hydrocarbon fragments results in significant surface coking above 500 K.

Low temperature 1,1,1-trichloroethane dehydrochlorination over Pt catalysts: from model surfaces to the real world

Fast X-ray photoelectron spectroscopy reveals efficient C-Cl activation of 1,1,1-trichloroethane occurs over platinum surfaces at 150 K, and in the presence of hydrogen, sustained ambient temperature dehydrochlorination to HCl and ethane is possible over supported Pt/Al2O3 catalysts.

NO adsorption on Rh(100). II. Stability of the adlayers

The composition, stability, and thermal evolution of nitric oxide on Rh(100) have been characterized by means of synchrotron radiation fast x-ray photoelectron spectroscopy and low-energy-electron diffraction. At 140 K, there is a single NO chemisorbed species (α2–NO) at saturation, forming a disordered phase which develops in an ordered p(4√×√)R45° structure after heating the layer to 373 K. A further annealing induces desorption and a progressive dissociation of the NO molecules, which is completed above 425 K, where a c(2×2) phase consisting of coadsorbed N and O atoms is observed. At low NO coverage, a different NO molecular species (α1–NO), characterized by ≈1.7 eV lower N1s binding energy, is detected on Rh(100). α1–NO is observed to undergo dissociation under the photon beam. The N1s line shape modifications due to irradiation by 500 eV photons were monitored in real time by using fast photoemission. The different stability of the α1–NO and α2–NO species is discussed.

Interaction of nitric oxide with Pt(1 0 0). A fast X-ray photoelectron spectroscopy study

The interaction of nitric oxide (NO) with the clean, reconstructed (1 0 0) surface of platinum is studied using synchrotron X-ray photoelectron spectroscopy. It is found that molecular adsorption at 200 K yields two different molecular NO species. Above 250 K, NO is found to adsorb both dissociatively and molecularly, giving rise to an oxygen/NO coadsorption structure with a molecular coverage that is half of that at 200 K. At 375 K, adsorption is found to be exclusively dissociative. Furthermore, it is found that NO dissociation yields two different atomic oxygen species. No significant coverage of atomic nitrogen is observed indicating fast combination of nitrogen atoms upon NO dissociation.

A fast x-ray photoelectron spectroscopy study of the adsorption and temperature-dependent decomposition of propene on Ni(100)

Using synchrotron radiation, the adsorption and decomposition of propene (C3H6) on the Ni(100) surface has been investigated in situ by time-resolved and temperature-programmed x-ray photoelectron spectroscopy. At 105 K, high-resolution C 1s spectra indicate precursor mediated occupation of a single adsorption state from submonolayer to monolayer coverage with evidence of adsorbate–adsorbate interactions and dispersed phase growth. High exposures lead to the formation of multilayers which desorb above 105 K leaving a chemisorbed monolayer. Between 105 and 150 K, a shift of the binding energies in the C 1s spectra is attributed to the transition from π- to di-σ-bonded propene. An abrupt change in the photoemission spectra occurs at 200 K due to the conversion of di-σ-bonded propene to a C3 intermediate containing a methyl group. Formation of this C2HxCH3 surface species is complete at 300 K and is immediately proceeded by dehydrogenation to carbidic carbon which is the final decomposition product above 370 K.

Nonlinear Behavior in the NO−H2Reaction over Ir(110) Studied by Fast X-ray Photoelectron Spectroscopy

The nonlinear behavior in the NO−H2 reaction over Ir(110) was studied with X-ray photoelectron spectroscopy (XPS). At a NO pressure of 7.7 × 10-8 mbar, three different H2/NO mixtures were examined ...

Evidence of repulsive interactions between NO, O, and N on Ir(110). A fast x-ray photoelectron spectroscopy study

The adsorption of NO on Ir(110) was studied in the temperature range from 200 to 500 K with fast x-ray photoelectron spectroscopy (XPS) using synchrotron radiation. Only three surface species were observed: molecular NO, atomic O, and atomic N. NO dissociation starts at temperatures higher than 300 K and molecular NO can coadsorb with Oads in the whole temperature region studied. By collecting O 1s and N 1s spectra within a few seconds we obtained information on the interaction between Nads, Oads, and NOads with increasing coadsorbate coverage. The Nads–Oads interaction has been found to be strongly repulsive. As a consequence, the Nads is destabilized already at moderate coverages and temperatures above 350 K leading to the removal of Nads from the surface in the form of N2 desorption.