Surface Science Experiments Research Articles

CO Adsorption on a Single-Atom Catalyst Stably Embedded in Graphene.

Confined single metal atoms in graphene-based materials have proven to be excellent catalysts for several reactions and promising gas sensing systems. However, whether the chemical activity arises from the specific type of metal atom or is a direct consequence of the confinement itself remains unclear. In this work, through a combined density functional theoryand experimental surface science study, we address this question by investigating Co and Ni single atoms embedded in graphene (Gr) on a Ni(111) support. These two single atom catalysts (SACs) exhibit opposite behavior toward carbon monoxide (CO) gas molecules: at RT, CO binds stably to Co, whereas it does not to Ni. We rationalize this difference by the energy position oftrapped metal dxz and dyz states involved in π backdonation to CO: while for Co, these states lie at the Fermi level, for Ni are located deep below it. This conclusion is corroborated by a proof-of-concept experiment, where a Gr/Ni(111) sample containing both stable Ni and Co single atoms was exposed to a CO partial pressure of 5 ‧ 10-7 mbar. Scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption (TPD) measurements confirm the selective adsorption of CO on Co at RT.

A simple cavity-enhanced laser-based heater for reflective samples.

Surface science instruments require excellent vacuum to ensure surface cleanliness; they also require control of sample temperature, both to clean the surface of contaminants and to control reaction rates at the surface, for example, for molecular beam epitaxy and studies of heterogeneous catalysis. Standard approaches to sample heating within high vacuum chambers involve passing current through filaments of refractory metals, which then heat the sample by convective, radiative, or electron bombardment induced heat transfer. Such hot filament methods lead to outgassing of molecules from neighboring materials that are inadvertently heated; they also produce electrons and ions that may interfere with other aspects of the surface science experiment. Hot filaments may even disintegrate when used in the presence of gases introduced to induce surface reactions on the sample. Optical heating using lasers can deliver energy directly to the sample, ensuring that only the sample is heated and surroundings within the vacuum chamber are not, while simultaneously eliminating the need for hot filaments. Despite this advantage, optical heating is not commonly employed-such methods are considered complex, expensive, and unreliable. More fundamentally, surface scientists are often interested in metallic samples, whose reflectivity may limit the efficiency of laser heating. In this paper, we describe a simple and inexpensive sample heater based on a commercial diode laser, whose heating efficiency is enhanced by a concave aluminum mirror placed behind the sample. The geometry of the reflector and sample ensures that a stable optical cavity is produced. Using only 26W of laser power directed to the sample with a fiber optic, a 1-cm diameter × 2-mm thick Pt sample could be heated to 1400K within 1min. Excellent programmable temperature control and long-term temperature stability are also demonstrated. Sample heating to 900 °C was performed with negligible increase in chamber pressure. The entire setup comprises components costing less than typical electron bombardment heaters.

Electron-induced deposition using Fe(CO)4MA and Fe(CO)5 - effect of MA ligand and process conditions.

The electron-induced decomposition of Fe(CO)4MA (MA = methyl acrylate), which is a potential new precursor for focused electron beam-induced deposition (FEBID), was investigated by surface science experiments under UHV conditions. Auger electron spectroscopy was used to monitor deposit formation. The comparison between Fe(CO)4MA and Fe(CO)5 revealed the effect of the modified ligand architecture on the deposit formation in electron irradiation experiments that mimic FEBID and cryo-FEBID processes. Electron-stimulated desorption and post-irradiation thermal desorption spectrometry were used to obtain insight into the fate of the ligands upon electron irradiation. As a key finding, the deposits obtained from Fe(CO)4MA and Fe(CO)5 were surprisingly similar, and the relative amount of carbon in deposits prepared from Fe(CO)4MA was considerably less than the amount of carbon in the MA ligand. This demonstrates that electron irradiation efficiently cleaves the neutral MA ligand from the precursor. In addition to deposit formation by electron irradiation, the thermal decomposition of Fe(CO)4MA and Fe(CO)5 on an Fe seed layer prepared by EBID was compared. While Fe(CO)5 sustains autocatalytic growth of the deposit, the MA ligand hinders the thermal decomposition in the case of Fe(CO)4MA. The heteroleptic precursor Fe(CO)4MA, thus, offers the possibility to suppress contributions of thermal reactions, which can compromise control over the deposit shape and size in FEBID processes.

Interrogating site dependent kinetics over SiO2-supported Pt nanoparticles

A detailed knowledge of reaction kinetics is key to the development of new more efficient heterogeneous catalytic processes. However, the ability to resolve site dependent kinetics has been largely limited to surface science experiments on model systems. Herein, we can bypass the pressure, materials, and temperature gaps, resolving and quantifying two distinct pathways for CO oxidation over SiO2-supported 2 nm Pt nanoparticles using transient pressure pulse experiments. We find that the pathway distribution directly correlates with the distribution of well-coordinated (e.g., terrace) and under-coordinated (e.g., edge, vertex) CO adsorption sites on the 2 nm Pt nanoparticles as measured by in situ DRIFTS. We conclude that well-coordinated sites follow classic Langmuir-Hinshelwood kinetics, but under-coordinated sites follow non-standard kinetics with CO oxidation being barrierless but conversely also slow. This fundamental method of kinetic site deconvolution is broadly applicable to other catalytic systems, affording bridging of the complexity gap in heterogeneous catalysis.

Insights into the Stability and Surface Termination of Topological Semimetal NbAs2

AbstractNbAs2, a topological semimetal, has stirred considerable interest for its potential usage in magnetic and fault‐tolerant quantum computation superconductor devices, owing to its superconductivity, enormous magnetoresistance, and anisotropic magneto‐transport attributes. Yet, its environmental stability, a crucial factor for practical applications, remains largely unexplored. Herein, a comprehensive examination of the stability and electronic properties of the (001) surface of NbAs2 utilizing density functional theory (DFT) and surface science experiments is conducted. The theoretical deductions reveal that As atoms, organized in a buckled honeycomb configuration, terminate the bare (001) surface, akin to the tensile blue arsenene monolayer along the armchair direction. This study further demonstrates that the oxidation barrier is particularly low (only 0.2 eV), highlighting that the (001) surface is highly prone to oxidation under standard conditions, forming a As2O5+Nb2O5/NbAs2 heterostructure. Additionally, it observes that oxidation adversely affects the electronic characteristics of the topological semimetal NbAs2. The conclusions underscore the need for NbAs2 to be managed under high vacuum conditions or to be encapsulated for any usage in the ambient atmosphere in order to retain its electronic properties for practical purposes.

Investigating Spillover Energy as a Descriptor for Single-Atom Alloy Catalyst Design.

The identification of thermodynamic descriptors of catalytic performance is essential for the rational design of heterogeneous catalysts. Here, we investigate how spillover energy, a descriptor quantifying whether intermediates are more stable at the dopant or host metal sites, can be used to design single-atom alloys (SAAs) for formic acid dehydrogenation. Using theoretical calculations, we identify NiCu as a SAA with favorable spillover energy and demonstrate that formate intermediates produced after the initial O-H activation are more stable at Ni sites where rate-determining C-H activation occurs. Surface science experiments demonstrated that NiCu(111) SAAs are more reactive than Cu(111) while they still follow the formate reaction pathway. However, reactor studies of silica-supported NiCu SAA nanoparticles showed only a modest improvement over Cu resulting from surface coverage effects. Overall, this study demonstrates the potential of engineering SAAs using spillover energy as a design parameter and highlights the importance of adsorbate-adsorbate interactions under steady-state operation.

Molecular Views on Fischer-Tropsch Synthesis.

For nearly a century, the Fischer-Tropsch (FT) reaction has been subject of intense debate. Various molecular views on the active sites and on the reaction mechanism have been presented for both Co- and Fe-based FT reactions. In the last 15 years, the emergence of a surface-science- and molecular-modeling-based bottom-up approach has brought this molecular picture a step closer. Theoretical models provided a structural picture of the Co catalyst particles. Recent surface science experiments and density functional theory (DFT) calculations highlighted the importance of realistic surface coverages, which can induce surface reconstruction and impact the stability of reaction intermediates. For Co-based FTS, detailed microkinetic simulations and mechanistic experiments are moving toward a consensus about the active sites and the reaction mechanism. The dynamic phase evolution of Fe-based catalysts under the reaction conditions complicates identification of the surface structure and the active sites. New techniques can help tackle the combinatorial complexity in these systems. Experimental and DFT studies have addressed the mechanism for Fe-based catalysts; the absence of a clear molecular picture of the active sites, however, limits the development of a molecular view of the mechanism. Finally, direct CO2 hydrogenation to long-chain hydrocarbons could present a sustainable pathway for FT synthesis.

A Priori Design of Dual-Atom Alloy Sites and Experimental Demonstration of Ethanol Dehydrogenation and Dehydration on PtCrAg.

Single-atom catalysts have received significant attention for their ability to enable highly selective reactions. However, many reactions require more than one adjacent site to align reactants or break specific bonds. For example, breaking a C-O or O-H bond may be facilitated by a dual site containing an oxophilic element and a carbophilic or "hydrogenphilic" element that binds each molecular fragment. However, design of stable and well-defined dual-atom sites with desirable reactivity is difficult due to the complexity of multicomponent catalytic surfaces. Here, we describe a new type of dual-atom system, trimetallic dual-atom alloys, which were designed via computation of the alloying energetics. Through a broad computational screening we discovered that Pt-Cr dimers embedded in Ag(111) can be formed by virtue of the negative mixing enthalpy of Pt and Cr in Ag and the favorable interaction between Pt and Cr. These dual-atom alloy sites were then realized experimentally through surface science experiments that enabled the active sites to be imaged and their reactivity related to their atomic-scale structure. Specifically, Pt-Cr sites in Ag(111) can convert ethanol, whereas PtAg and CrAg are unreactive toward ethanol. Calculations show that the oxophilic Cr atom and the hydrogenphilic Pt atom act synergistically to break the O-H bond. Furthermore, ensembles with more than one Cr atom, present at higher dopant loadings, produce ethylene. Our calculations have identified many other thermodynamically favorable dual-atom alloy sites, and hence this work highlights a new class of materials that should offer new and useful chemical reactivity beyond the single-atom paradigm.

Activating lattice oxygen of single-layer ZnO for the catalytic oxidation reaction.

Tuning an oxide/metal interface is of critical importance for the performance enhancement of many heterogeneous catalytic reactions. However, catalytic oxidation occurring at the interface between non-reducible oxide and metal has been challenging, since non-reducible oxides hardly lose their lattice oxygen (OL) or dissociate O2 from the gas phase. In this work, a ZnO monolayer film on Au(111) is used as an inverse catalyst to investigate CO oxidation occurring at the ZnO/Au(111) interface via high pressure scanning tunneling microscopy. Surface science experiments indicate that oxygen intercalation under the ZnO monolayer film, termed ZnO/O/Au(111), can be achieved via a surface reaction with 1 × 10-6 mbar O3. Subsequent exposure of the formed ZnO/O/Au(111) surface to mbar CO at room temperature leads to the recovery of the pristine ZnO/Au(111) surface. Theoretical calculations reveal that OL adjacent to intercalated oxygen (Oint) is activated due to the OL-Zn-Oint bonding and surface corrugation, which can be directly involved in CO oxidation. Subsequently, Oint migrates to the formed oxygen vacancy from the subsurface resuming the pristine ZnO structure. These results thus reveal that oxygen intercalation underneath single-layer ZnO will strongly boost the oxidation reaction via activating adjacent lattice oxygen atoms.

Graphene at Liquid Copper Catalysts: Atomic-Scale Agreement of Experimental and First-Principles Adsorption Height.

Liquid metal catalysts have recently attracted attention for synthesizing high-quality 2D materials facilitated via the catalysts' perfectly smooth surface. However, the microscopic catalytic processes occurring at the surface are still largely unclear because liquid metals escape the accessibility of traditional experimental and computational surface science approaches. Hence, numerous controversies are found regarding different applications, with graphene (Gr) growth on liquid copper (Cu) as a prominent prototype. In this work, novel in situ and in silico techniques are employed to achieve an atomic-level characterization of the graphene adsorption height above liquid Cu, reaching quantitative agreement within 0.1 Å between experiment and theory. The results are obtained via in situ synchrotron X-ray reflectivity (XRR) measurements over wide-range q-vectors and large-scale molecular dynamics simulations based on efficient machine-learning (ML) potentials trained to first-principles density functional theory (DFT) data. The computational insight is demonstrated to be robust against inherent DFT errors and reveals the nature of graphene binding to be highly comparable at liquid Cu and solid Cu(111). Transporting the predictive first-principles quality via ML potentials to the scales required for liquid metal catalysis thus provides a powerful approach to reach microscopic understanding, analogous to the established computational approaches for catalysis at solid surfaces.

Effect of temperature on CO oxidation over Pt(111) in two-dimensional confinement.

Confined catalysis between a two-dimensional (2D) cover and metal surfaces has provided a unique environment with enhanced activity compared to uncovered metal surfaces. Within this 2D confinement, weakened adsorption and lowered activation energies were observed using surface science experiments and density functional theory (DFT) calculations. Computationally, the role of electronic and mechanical factors responsible for the improved activity was deduced only from static DFT calculations. This demands a detailed investigation on the dynamics of reactions under 2D confinement, including temperature effects. In this work, we study CO oxidation on a 2D graphene covered Pt(111) surface at 90 and 593K using DFT-based ab initio molecular dynamics simulations starting from the transition state configuration. We show that CO oxidation in the presence of a graphene cover is substantially enhanced (2.3 times) at 90K. Our findings suggest that 2D confined spaces can be used to enhance the activity of chemical reactions, especially at low temperatures.

Stabilizing Oxide Nanolayer via Interface Confinement and Surface Hydroxylation.

Surface hydroxylation over oxide catalysts often occurs in many catalytic processes involving H2 and H2O, which is considered to play an important role in elementary steps of the reactions. Here, monolayer CoO and CoOHx nanoislands on Pt(111) are used as inverse model catalysts to study the effect of surface hydroxylation on the stability of Co oxide overlayers in O2. Surface science experiments indicate that hydroxyl groups formed on CoO nanoislands produced by deuterium-spillover can enhance oxidation resistance of the Co oxide nanostructures. Theoretical calculation shows that the interfacial adhesion between CoO and Pt is linearly strengthened with the increasing hydroxylation degree of CoO surface. Thus, the interface confinement effect between CoO and Pt can be enhanced by the surface hydroxylation due to the more reduced Co ions and stronger Co-Pt bonding at the CoOHx/Pt interface.

Evidence of a Tetrahedrally Coordinated RuO4 Surface Complex on RuO2(100): Density Functional Theory and Beyond

RuO2(100), an efficient low-temperature oxidation model catalyst, is able to undergo a c(2 × 2) reconstruction with a so far unknown surface structure that is accompanied by the loss of its catalytic activity. Here, the surface structure of the c(2 × 2) reconstruction of RuO2(100) is predicted by ab initio molecular dynamics simulations and shown to be consistent with available surface science experiments from the literature, including scanning tunneling microscopy (STM) images, low-energy electron diffraction (LEED) intensity versus voltage experiments, and thermal desorption experiments of O2. Mechanistically, the c(2 × 2) reconstruction starts from a simple c(2 × 2) overlayer structure of on-top O on RuO2(100), where the remaining undercoordinated surface Ru centers shift laterally toward the on-top O position, thereby breaking two Ru–O back bonds to lattice oxygen and forming a new Ru–O bond with on-top O. This leads to the formation of a tetrahedrally coordinated surface species Ru4f, a process that is activated by 0.95 eV and that results in an energy stabilization of 0.66 eV. The c(2 × 2) surface structure can readily explain the lack of activity in catalytic CO oxidation. The CO molecule is much more weakly bound on RuO2(100)-c(2 × 2) reconstruction than on the RuO2(110) or the RuO2(100)-(1 × 1) surface, and in addition, the Ru4f centers are too far apart to allow for O2 activation. The identified Ru4f surface species is expected to play a prevailing role as precursor species in the missing thermal and electrochemical stability of RuO2 under oxidizing reaction conditions by forming volatile RuO4.

Periodic Trends in Adsorption Energies around Single-Atom Alloy Active Sites.

Single-atom alloys (SAAs) make up a special class of alloy surface catalysts that offer well-defined, isolated active sites in a more inert metal host. The dopant sites are generally assumed to have little or no influence on the properties of the host metal, and transport of chemical reactants and products to and from the dopant sites is generally assumed to be facile. Here, by performing density functional theory calculations and surface science experiments, we identify a new physical effect on SAA surfaces, whereby adsorption is destabilized by ≤300 meV on host sites within the perimeter of the reactive dopant site. We identify periodic trends for this behavior and demonstrate a zone of exclusion around the reactive sites for a range of adsorbates and combinations of host and dopant metals. Experiments confirm an increased barrier for diffusion of CO toward the dopant on a RhCu SAA. This effect offers new possibilities for understanding and designing active sites with tunable energetic landscapes surrounding them.

Tuning the electronic properties of a clean TiO2(1 1 0) surface via repeated sputtering and annealing: A KPFM and LC-AFM study

Repeated sputtering and annealing are standard preparation methods for obtaining a stoichiometric TiO2(110) surface for surface science experiments. However, both processes result in a reduction in TiO2 crystal when used separately, leading to the modification of the physical and chemical properties of oxide materials. Our investigation aims to determine how these two processes affect the electronic properties of the surface and subsurface regions at the nanometer scale. To accomplish this goal, we utilized local microscopy (Kelvin probe force microscopy and local-conductivity atomic force microscopy) and spectroscopy methods (X-ray photoelectron spectroscopy and secondary ion mass spectrometry). We found that repeated sputtering and annealing does, in fact, affect both the conductivity and work function of the surface. The work function, as well as conductivity, increase with increasing number of cycles, but then reach a plateau. Furthermore, we show that the way the surface is prepared, using multiple cycles or one cycle of equivalent ion-beam fluence, matters. We attribute the differences in the crystal properties to the dynamics of stoichiometric changes during sputtering and subsequent annealing which we illustrate using secondary ion mass spectroscopy, which shows that after multiple cycles the subsurface layer is modified, even though XPS shows a stoichiometric surface.

Atomistic Descriptions of Gas-Surface Interactions on Tin Dioxide

Historically, in gas sensing literature, the focus on “mechanisms” has been on oxygen species chemisorbed (ionosorbed) from the ambient atmosphere, but what these species actually represent and the location of the adsorption site on the surface of the solid are typically not well described. Recent advances in computational modelling and experimental surface science provide insights on the likely mechanism by which oxygen and other species interact with the surface of SnO2, providing insight into future directions for materials design and optimisation. This article reviews the proposed models of adsorption and reaction of oxygen on SnO2, including a summary of conventional evidence for oxygen ionosorption and recent operando spectroscopy studies of the atomistic interactions on the surface. The analysis is extended to include common target and interfering reducing gases, such as CO and H2, cross-interactions with H2O vapour, and NO2 as an example of an oxidising gas. We emphasise the importance of the surface oxygen vacancies as both the preferred adsorption site of many gases and in the self-doping mechanism of SnO2.

CoCrFeNi High-Entropy Alloy as an Enhanced Hydrogen Evolution Catalyst in an Acidic Solution.

High-entropy alloys (HEAs) have intriguing material properties, but their potential as catalysts has not been widely explored. Based on a concise theoretical model, we predict that the surface of a quaternary HEA of base metals, CoCrFeNi, should go from being nearly fully oxidized except for pure Ni sites when exposed to O2 to being partially oxidized in an acidic solution under cathodic bias, and that such a partially oxidized surface should be more active for the electrochemical hydrogen evolution reaction (HER) in acidic solutions than all the component metals. These predictions are confirmed by electrochemical and surface science experiments: the Ni in the HEA is found to be most resistant to oxidation, and when deployed in 0.5 M H2SO4, the HEA exhibits an overpotential of only 60 mV relative to Pt for the HER at a current density of 1 mA/cm2.

Critical Role of Thermal Fluctuations for CO Binding on Electrocatalytic Metal Surfaces.

This work considers the evaluation of density functional theory (DFT) when comparing against experimental observations of CO binding trends on the strong binding Pt(111) and intermediate binding Cu(111) and for weak binding Ag(111) and Au(111) surfaces important in electrocatalysis. By introducing thermal fluctuations using appropriate statistical mechanical NVT and NPT ensembles, we find that the RPBE and B97M-rV DFT functionals yield qualitatively better metal surface strain trends and CO enthalpies of binding for Cu(111) and Pt(111) than found at 0 K, thereby correcting the overbinding by 0.2 to 0.3 eV to yield better agreement with the enthalpies determined from experiment. The importance of dispersion effects are manifest for the weak CO binding Ag(111) and Au(111) surfaces at finite temperatures in which the RPBE functional does not bind CO at all, while the B97M-rV functional shows that the CO–metal interactions are a mixture of chemisorbed and physisorbed species with binding enthalpies that are within ∼0.05 eV of experiment. Across all M(111) surfaces, we show that the B97M-rV functional consistently predicts the correct atop site preference for all metals due to thermally induced surface distortions that preferentially favor the undercoordinated site. This study demonstrates the need to fully account for finite temperature fluctuations to make contact with the binding enthalpies from surface science experiments and electrocatalysis applications.

Factors influencing surface carbon contamination in ambient-pressure x-ray photoelectron spectroscopy experiments

Carbon contamination is a notorious issue that has an enormous influence on surface science experiments, especially in near-atmospheric conditions. While it is often mentioned in publications when affecting an experiment’s results, it is more rarely analyzed in detail. We performed ambient-pressure x-ray photoelectron spectroscopy experiments toward examining the build-up of adventitious carbon species (both inorganic and hydrocarbons) on a clean and well-prepared surface using large-scale (50 × 10 mm2) rutile TiO2(110) single crystals exposed to water vapor and liquid water. Our results highlight how various factors and environmental conditions, such as beam illumination, residual gas pressure and composition, and interaction with liquid water, could play roles in the build-up of carbon on the surface. It became evident that beam-induced effects locally increase the amount of carbon in the irradiated area. Starting conditions that are independent of light irradiation determine the initial overall contamination level. Surprisingly, the rate of beam-induced carbon build-up does not vary significantly for different starting experimental conditions. The introduction of molecular oxygen in the order of 10 mbar allows for fast surface cleaning during x-ray illumination. The surface carbon contamination can be completely removed when the oxygen partial pressure is comparable to the partial pressure of water vapor in the millibar pressure range, as was tested by exposing the TiO2(110) surface to 15 mbar of water vapor and 15 mbar of molecular O2 simultaneously. Furthermore, our data support the hypothesis that the progressive removal of carbon species from the chamber walls by competitive adsorption of water molecules takes place following repeated exposure to water vapor. We believe that our findings will be useful for future studies of liquid-solid interfaces using tender x rays, where carbon contamination plays a significant role.

Carbon contamination reduced for ambient-pressure X-ray spectroscopy

Approaches to removing carbon contamination from titanium dioxide samples could improve surface science experiments.