Origin of hydroxyl pair formation on reduced anatase TiO2(101).

The interaction of water with metal oxide surfaces is of key importance to several research fields and applications. Because of its ability to photo-catalyze water splitting, reducible anatase TiO2 (a-TiO2) is of particular interest. Here, we combine experiments and theory to study the dissociation of water on bulk-reduced a-TiO2(101). Following large water exposures at room temperature, point-like protrusions appear on the a-TiO2(101) surface, as shown by scanning tunneling microscopy (STM). These protrusions originate from hydroxyl pairs, consisting of terminal and bridging OH groups, OHt/OHb, as revealed by infrared reflection absorption spectroscopy (IRRAS) and valence band experiments. Utilizing density functional theory (DFT) calculations, we offer a comprehensive model of the water/a-TiO2(101) interaction. This model also explains why the hydroxyl pairs are thermally stable up to ∼480 K.

Electrically Tunable Reactivity of Substrate-Supported Cobalt Oxide Nanocrystals.

First-row transition metal oxides are promising materials for catalyzing the oxygen evolution reaction. Surface sensitive techniques provide a unique perspective allowing the study of the structure, adsorption sites, and reactivity of catalysts at the atomic scale, which furnishes rationalization and improves the design of highly efficient catalytic materials. Here, a scanning probe microscopy study complemented by density functional theory on the structural and electronic properties of CoO nanoislands grown on Au(111) is reported. Two distinct phases are observed: The most extended displays a Moiré pattern (α-region), while the less abundant is 1Co:1Au coincidental (ß-region). As a result of the surface registry, in the ß-region the oxide adlayer is compressed by 9%, increasing the unoccupied local density of states and enhancing the selective water adsorption at low temperature through a cobalt inversion mechanism. Tip-induced voltage pulses irreversibly transform α- into ß-regions, thus opening avenues to modify the structure and reactivity of transition metal oxides by external stimuli like electric fields.

The cobalt oxidation state in preferential CO oxidation on CoOx/Pt(111) investigated by operando X-ray photoemission spectroscopy.

The combination of a reducible transition metal oxide and a noble metal such as Pt often leads to active low-temperature catalysts for the preferential oxidation of CO in excess H2 gas (PROX reaction). While CO oxidation has been investigated for such systems in model studies, the added influence of hydrogen gas, representative of PROX, remains less explored. Herein, we use ambient pressure scanning tunneling microscopy and ambient pressure X-ray photoelectron spectroscopy on a CoOx/Pt(111) planar model catalyst to analyze the active phase and the adsorbed species at the CoOx/Pt(111) interface under atmospheres of CO and O2 with a varying partial pressure of H2 gas. By following the evolution of the Co oxidation state as the catalyst is brought to a reaction temperature of above 150 °C, we determine that the active state is characterized by the transformation from planar CoO with Co in the 2+ state to a mixed Co2+/Co3+ phase at the temperature where CO2 production is first observed. Furthermore, our spectroscopy observations of the surface species suggest a reaction pathway for CO oxidation, proceeding from CO exclusively adsorbed on Co2+ sites reacting with the lattice O from the oxide. Under steady state CO oxidation conditions (CO/O2), the mixed oxide phase is replenished from oxygen incorporating into cobalt oxide nanoislands. In CO/O2/H2, however, the onset of the active Co2+/Co3+ phase formation is surprisingly sensitive to the H2 pressure, which we explain by the formation of several possible hydroxylated intermediate phases that expose both Co2+ and Co3+. This variation, however, has no influence on the temperature where CO oxidation is observed. Our study points to the general importance of a dynamic reducibility window of cobalt oxide, which is influenced by hydroxylation, and the bonding strength of CO to the reduced oxide phase as important parameters for the activity of the system.

Molecular Nanowire Bonding to Epitaxial Single-Layer MoS2 by an On-Surface Ullmann Coupling Reaction.

Lateral heterostructures consisting of 2D transition metal dichalcogenides (TMDCs) directly interfaced with molecular networks or nanowires can be used to construct new hybrid materials with interesting electronic and spintronic properties. However, chemical methods for selective and controllable bond formation between 2D materials and organic molecular networks need to be developed. As a demonstration of a self-assembled organic nanowire-TMDC system, a method to link and interconnect epitaxial single-layer MoS2 flakes with organic molecules is demonstrated. Whereas pristine epitaxial single-layer MoS2 has no affinity for molecular attachment, it is found that single-layer MoS2 will selectively bind the organic molecule 2,8-dibromodibenzothiophene (DBDBT) in a surface-assisted Ullmann coupling reaction when the MoS2 has been activated by pre-exposing it to hydrogen. Atom-resolved scanning tunneling microscopy (STM) imaging is used to analyze the bonding of the nanowires, and thereby it is revealed that selective bonding takes place on a specific S atom at the corner site between the two types of zig-zag edges available in a hexagonal single layer MoS2 sheet. The method reported here successfully combining synthesis of epitaxial TMDCs and Ullmann coupling reactions on surfaces may open up new synthesis routes for 2D organic-TMDC hybrid materials.

Adsorption and reaction of methanol on Fe3O4(001).

The interaction of methanol with iron oxide surfaces is of interest due to its potential in hydrogen storage and from a fundamental perspective as a chemical probe of reactivity. We present here a study examining the adsorption and reaction of methanol on magnetite Fe3O4(001) at cryogenic temperatures using a combination of temperature programmed desorption, x-ray photoelectron spectroscopy, and scanning tunneling microscopy. The methanol desorption profile from Fe3O4(001) is complex, exhibiting peaks at 140 K, 173 K, 230 K, and 268 K, corresponding to the desorption of intact methanol, as well as peaks at 341 K and 495 K due to the reaction of methoxy intermediates. The saturation of a monolayer of methanol corresponds to ∼5 molecules/unit cell (u.c.), which is slightly higher than the number of surface octahedral iron atoms of 4/u.c. We probe the kinetics and thermodynamics of the desorption of molecular methanol using inversion analysis. The deconvolution of the complex desorption profile into individual peaks allows for calculations of both the desorption energy and the prefactor of each feature. The initial 0.7 methanol/u.c. reacts to form methoxy and hydroxy intermediates at 180 K, which remain on the surface above room temperature after intact methanol has desorbed. The methoxy species react via one of two channels, a recombination reaction with surface hydroxyls to form additional methanol at ∼350 K and a disproportionation reaction to form methanol and formaldehyde at ∼500 K. Only 20% of the methoxy species undergo the disproportionation reaction, with most of them reacting via the 350 K pathway.

Structural and electronic properties of Fe dopants in cobalt oxide nanoislands on Au(111).

Mixed metal oxides of earth-abundant 3d transition metals are an interesting class of materials that show interesting magnetic properties and a significant synergistic effect as catalysts for electrochemical oxygen evolution compared to simple unary oxides. However, the exact atomic-scale nature of such mixed oxide phases and the link to their interesting physico-chemical properties are poorly understood. Here, a combination of scanning tunneling microscopy and x-ray photoemission spectroscopy reveals that Fe species embed in a facile way into CoO bilayers on Au(111) resulting in an Fe doped oxide. Density functional theory and the spectroscopic fingerprint from x-ray photoemission spectroscopy reveal that the Fe dopants in the cobalt oxide matrix assume a higher oxidation state than in the structurally corresponding unary bilayer oxide. Furthermore, the substituted Fe is structurally displaced further away from the Au than the metal in either of the corresponding pure unary oxides. Both O and to a smaller extent Co in the nearest coordination shell are also structurally and electronically perturbed. The interesting effects observed in the bilayer binary oxides may enable a better fundamental understanding of the nature of doping of metal oxides, in general, and promotion effects in catalytic applications.

Water Dissociation and Hydroxyl Ordering on Anatase TiO_{2}(001)-(1×4).

We studied the interaction of water with the anatase TiO_{2}(001) surface by means of scanning tunneling microscopy, x-ray photoelectron spectroscopy, and density functional theory calculations. Water adsorbs dissociatively on the ridges of a (1×4) reconstructed surface, resulting in a (3×4) periodic structure of hydroxyl pairs. We observed this process at 120 K, and the created hydroxyls desorb from the surface by recombination to water, which occurs below 300 K. Our calculations reveal the water dissociation mechanism and uncover a very pronounced dependence on the coverage. This strong coverage dependence is explained through water-induced reconstruction on anatase TiO_{2}(001)-(1×4). The high intrinsic reactivity of the anatase TiO_{2}(001) surface towards water observed here is fundamentally different from that seen on other surfaces of titania and may explain its high catalytic activity in heterogeneous catalysis and photocatalysis.

NH3 adsorption on anatase-TiO2(101).

The adsorption of ammonia on anatase TiO2 is of fundamental importance for several catalytic applications of TiO2 and for probing acid-base interactions. Utilizing high-resolution scanning tunneling microscopy (STM), synchrotron X-ray photoelectron spectroscopy, temperature-programmed desorption (TPD), and density functional theory (DFT), we identify the adsorption mode and quantify the adsorption strength on the anatase TiO2(101) surface. It was found that ammonia adsorbs non-dissociatively as NH3 on regular five-fold coordinated titanium surface sites (5f-Ti) with an estimated exothermic adsorption energy of 1.2 eV for an isolated ammonia molecule. For higher adsorbate coverages, the adsorption energy progressively shifts to smaller values, due to repulsive intermolecular interactions. The repulsive adsorbate-adsorbate interactions are quantified using DFT and autocorrelation analysis of STM images, which both showed a repulsive energy of ∼50 meV for nearest neighbor sites and a lowering in binding energy for an ammonia molecule in a full monolayer of 0.28 eV, which is in agreement with TPD spectra.

The Structure of the Cobalt Oxide/Au Catalyst Interface in Electrochemical Water Splitting.

The catalytic synergy between cobalt oxide and gold leads to strong promotion of the oxygen evolution reaction (OER)-one half-reaction of electrochemical water splitting. However, the mechanism behind the enhancement effect is still not understood, in part due to a missing structural model of the active interface. Using a novel interplay of cyclic voltammetry (CV) for electrochemistry integrated with scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) on an atomically defined cobalt oxide/Au(111) system, we reveal here that the supporting gold substrate uniquely favors a flexible cobalt-oxyhydroxide/Au interface in the electrochemically active potential window and thus suppresses the formation of less active bulk cobalt oxide morphologies. The findings substantiate why optimum catalytic synergy is obtained for oxide coverages on gold close to or below one monolayer, and provide the first morphological description of the active phase during electrocatalysis.

Single-layer MoS2 formation by sulfidation of molybdenum oxides in different oxidation states on Au(111).

The sulfidation of a MoO3 precursor into MoS2 is an important step in the preparation of catalysts for the hydrodesulfurization process that is widely utilized in oil refineries. Molybdenum oxides are also the most commonly used precursors for MoS2 growth in, e.g., the synthesis of novel two-dimensional materials. In the present study, we investigate the transformation of MoOx into MoS2 on a model Au(111) surface through sulfidation in H2S gas atmosphere using in situ scanning tunneling microscopy and X-ray photoemission spectroscopy. We find that progressive annealing steps of physical vapor deposited MoO3 powder allow us to control the stoichiometry and oxidation state of the precursor oxide. Subsequently, we investigate the sulfidation of the compounds ranging from pure low-oxygen Mo to fully oxidized MoO3 oxide sulfidation using two different methods. We find that the prerequisite for the efficient formation of MoS2 is that Mo stays in the highest Mo6+ state before sulfidation, whereas the presence of the reduced MoOx phase impedes the MoS2 growth. We also find that it is more efficient to form MoS2 by post-sulfidation of MoOx rather than its reactive deposition in H2S gas, which leads to rather stable amorphous oxysulfide phases.

Gold-supported two-dimensional cobalt oxyhydroxide (CoOOH) and multilayer cobalt oxide islands.

In the present study, we investigate the facile conversion of Co-O bilayer islands on a Au(111) surface into preferentially O-Co-O trilayers in an oxygen atmosphere and O-Co-O-Co-O multilayers at elevated temperature. We characterize and compare the island morphologies with scanning tunneling microscopy, X-ray photoemission spectroscopy (XPS) and valence band spectroscopy, and show that the cobalt oxidation state changes from Co2+ in bilayers to purely Co3+ in trilayers and a mixture of Co2+ and Co3+ in the multilayer morphology. In contrast to bilayers and multilayers, the trilayer structure appears to grow pseudomorphic with the Au(111) substrate, and in addition we reveal the presence of a hydroxyl overlayer on this island type as evidenced by the appearance of a superstructure in STM correlated with the fingerprints of OH species in XPS and valence band spectroscopy. The obtained layered morphology consisting of hydroxylated trilayer islands is identical to an exfoliated sheet of the ß-CoOOH which is proposed to be the active phase of the cobalt oxide oxygen evolution reaction catalyst present in the electrochemical environment, and we note that this synthesized structure thus could serve as a valuable model catalyst.

Facile embedding of single vanadium atoms at the anatase TiO2(101) surface.

To understand the structure-reactivity relationships for mixed-metal oxide catalysts, well-defined systems are required. Mixtures of vanadia and titania (TiO2) are of particular interest for application in heterogeneous catalysis, with TiO2 often acting as the support. By utilizing high-resolution scanning tunneling microscopy, we studied the interaction of vanadium (V) with the anatase TiO2(101) surface in the sub-monolayer regime. At 80 K, metallic V nucleates into homogeneously distributed clusters onto the terraces with no preference for nucleation at the step edges. However, embedding of single V atoms into TiO2 occurs following annealing at room temperature. In conjunction with X-ray photoelectron spectroscopy data and density functional theory calculations, we propose that monomeric V atoms occupy positions of regular surface Ti sites, i.e., Ti atoms are substituted by V atoms.

Effects of particle size and edge structure on the electronic structure, spectroscopic features, and chemical properties of Au(111)-supported MoS2 nanoparticles.

Materials based on MoS2 are widely used as catalysts and their structure usually consists of single-layered MoS2 nanoparticles whose edges are known to constitute the catalytically active sites. Methods based on density functional theory are used in this work to calculate the electronic structure of representative computational models of MoS2 nanoparticles supported on Au(111). By considering nanoparticles with different edge-terminations, compositions, and sizes, we describe how the electronic structure, Mo3d core-level shifts, and chemical properties (i.e. H adsorption and S vacancy formation) depend on the MoS2 nanoparticle size and structure. In addition, site-specific properties, largely inaccessible when using only slab models of MoS2 edges, are reported, which reveal that the edge sites are not uniform along the nanoparticle and largely depend on the proximity to the corners of the triangular NPs, especially when interacting with a metallic support. Furthermore, a structural motif where H atoms adsorb favourably in a bridging position between two Mo atoms is proposed as an active site for the hydrogen evolution reaction.

The reaction mechanism for the SCR process on monomer V(5+) sites and the effect of modified Brønsted acidity.

The energetics, structures and activity of a monomeric VO3H/TiO2(001) catalyst are investigated for the selective catalytic reduction (SCR) reaction by the use of density functional theory (DFT). Furthermore we study the influences of a dopant substitute in the TiO2 support and its effects on the known properties of the SCR system such as Brønsted acidity and reducibility of vanadium. We find for the reduction part of the SCR mechanism that it involves two Ti-O-V oxygen sites. One is a hydroxyl possessing Brønsted acidity which contributes to the formation of NH4(+), while the other accepts a proton which charge stabilizes the reduced active site. In the reduction the proton is donated to the latter due to a reaction between NH3 and NO that forms a H2NNO molecule which decomposes into N2(g) and H2O(g). A dopant substitution of 10 different dopants: Si, Ge, Se, Zr, Sn, Te, Hf, V, Mo and W at each of the sites, which participate in the reaction, modifies the energetics and therefore the SCR activity. We find that Brønsted acidity is a descriptor for the SCR activity at low temperatures. Based on this descriptor we find that Zr, Hf and Sn have a positive effect as they decrease the activation energy for the SCR reaction.

Observation of Ultrafast Free Carrier Dynamics in Single Layer MoS2.

The dynamics of excited electrons and holes in single layer (SL) MoS2 have so far been difficult to disentangle from the excitons that dominate the optical response of this material. Here, we use time- and angle-resolved photoemission spectroscopy for a SL of MoS2 on a metallic substrate to directly measure the excited free carriers. This allows us to ascertain a direct quasiparticle band gap of 1.95 eV and determine an ultrafast (50 fs) extraction of excited free carriers via the metal in contact with the SL MoS2. This process is of key importance for optoelectronic applications that rely on separated free carriers rather than excitons.

Synthesis of Epitaxial Single-Layer MoS2 on Au(111).

We present a method for synthesizing large area epitaxial single-layer MoS2 on the Au(111) surface in ultrahigh vacuum. Using scanning tunneling microscopy and low energy electron diffraction, the evolution of the growth is followed from nanoscale single-layer MoS2 islands to a continuous MoS2 layer. An exceptionally good control over the MoS2 coverage is maintained using an approach based on cycles of Mo evaporation and sulfurization to first nucleate the MoS2 nanoislands and then gradually increase their size. During this growth process the native herringbone reconstruction of Au(111) is lifted as shown by low energy electron diffraction measurements. Within the MoS2 islands, we identify domains rotated by 60° that lead to atomically sharp line defects at domain boundaries. As the MoS2 coverage approaches the limit of a complete single layer, the formation of bilayer MoS2 islands is initiated. Angle-resolved photoemission spectroscopy measurements of both single and bilayer MoS2 samples show a dramatic change in their band structure around the center of the Brillouin zone. Brief exposure to air after removing the MoS2 layer from vacuum is not found to affect its quality.

Correlation between stoichiometry and surface structure of the polar MgAl2O4(100) surface as a function of annealing temperature.

The correlation between surface structure, stoichiometry and atomic occupancy of the polar MgAl2O4(100) surface has been studied with an interplay of noncontact atomic force microscopy, X-ray photoelectron spectroscopy and surface X-ray diffraction under ultrahigh vacuum conditions. The Al/Mg ratio is found to significantly increase as the surface is sputtered and annealed in oxygen at intermediate temperatures ranging from 1073-1273 K. The Al excess is explained by the observed surface structure, where the formation of nanometer-sized pits and elongated patches with Al terminated step edges contribute to stabilizing the structure by compensating surface polarity. Surface X-ray diffraction reveals a reduced occupancy in the top two surface layers for both Mg, Al, and O and, moreover, vacancies are preferably located in octahedral sites, indicating that Al and Mg ions interchange sites. The excess of Al and high concentration of octahedral vacancies, very interestingly, indicates that the top few surface layers of the MgAl2O4(100) adopts a surface structure similar to that of a spinel-like transition Al2O3 film. However, after annealing at a high temperature of 1473 K, the Al/Mg ratio restores to its initial value, the occupancy of all elements increases, and the surface transforms into a well-defined structure with large flat terraces and straight step edges, indicating a restoration of the surface stoichiometry. It is proposed that the tetrahedral vacancies at these high temperatures are filled by Mg from the bulk, due to the increased mobility at high annealing temperatures.

Atomic structure of a spinel-like transition Al2O3(100) surface.

We study a crystalline epitaxial alumina thin film with the characteristics of a spinel-type transition Al2O3(100) surface by using atom-resolved noncontact atomic force microscopy and density functional theory. It is shown that the films are terminated by an Al-O layer rich in Al vacancies, exhibiting a strong preference for surface hydroxyl group formation in two configurations. The transition alumina films are crystalline and perfectly stable in ambient atmospheres, a quality which is expected to open the door to new fundamental studies of the surfaces of transition aluminas.

Visualizing the gas-sensitive structure of the CuZn surface in methanol synthesis catalysis.

Methanol formation over Cu/ZnO catalysts is linked with a catalytically active phase created by contact between Cu nanoparticles and Zn species whose chemical and structural state depends on reaction conditions. Herein, we use variable-temperature scanning tunneling microscopy at elevated pressure conditions combined with X-ray photoelectron spectroscopy measurements to investigate the surface structures and chemical states that evolve when a CuZn/Cu(111) surface alloy is exposed to reaction gas mixtures. In CO2 hydrogenation conditions, Zn stays embedded in the CuZn surface, but once CO gas is added to the mixture, the Zn segregates onto the Cu surface. The Zn segregation is CO-induced, and establishes a new dynamic state of the catalyst surface where Zn is continually exchanged at the Cu surface. Candidates for the migrating few-atom Zn clusters are further identified in time-resolved imaging series. The findings point to a significant role of CO affecting the distribution of Zn in the multiphasic ZnO/CuZn/Cu catalysts.

Morphology and atomic-scale structure of single-layer WS2 nanoclusters.

Two-dimensional sheets of transition metal (Mo and W) sulfides are attracting strong attention due to the unique electronic and optical properties associated with the material in its single-layer form. The single-layer MoS2 and WS2 are already in widespread commercial use in catalytic applications as both hydrotreating and hydrocracking catalysts. Consequently, characterization of the morphology and atomic structure of such particles is of utmost importance for the understanding of the catalytic active phase. However, in comparison with the related MoS2 system only little is known about the fundamental properties of single-layer WS2 (tungstenite). Here, we use an interplay of atom-resolved Scanning Tunneling Microscopy (STM) studies of Au(111)-supported WS2 nanoparticles and calculated edge structures using Density Functional Theory (DFT) to reveal the equilibrium morphology and prevalent edge structures of single-layer WS2. The STM results reveal that the single layer S-W-S sheets adopt a triangular equilibrium shape under the sulfiding conditions of the synthesis, with fully sulfided edges. The predominant edge structures are determined to be the (101[combining macron]0) W-edge, but for the smallest nanoclusters also the (1[combining macron]010) S-edges become important. DFT calculations are used to construct phase diagrams of the WS2 edges, and describe their sulfur and hydrogen coordination under different conditions, and in this way shed light on the catalytic role of WS2 edges.