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.

Water dissociation on mixed Co-Fe oxide bilayer nanoislands on Au(111).

We investigate the hydroxylation behaviour of mixed Co-Fe oxide nanoislands synthesized on a Au(111) surface under exposure to water vapour at vacuum conditions. The pure Co and Fe bilayer oxides both become hydroxylated by water exposure in vacuum conditions, albeit to a very different extent. It is however an open question how mixed oxides, exposing sites with a mixed coordination to Fe and Co, behave. By forming surface O species with a mixed Fe/Co coordination, we can investigate the nature of such sites. By means of scanning tunnelling microscopy and x-ray photoelectron spectroscopy, we characterize a series of Co-Fe oxides samples with different Fe contents at the atomic scale and observe a scaling of the hydroxylation degree with the amount of Fe inside the Co-Fe oxides. Our results indicate that the Fe dopants within the Co-Fe oxides have opposing effects on edge and basal plane sites modifying the maximum hydroxylation degree of pure cobalt oxide, perturbing the original binding sites of H, releasing the absorbed H or blocking the diffusion pathway of H.

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 Effect of Fe Dopant Location in Co(Fe)OOHx Nanoparticles for the Oxygen Evolution Reaction.

The addition of iron (Fe) can in certain cases have a strong positive effect on the activity of cobalt and nickel oxide nanoparticles in the electrocatalytic oxygen evolution reaction (OER). The reported optimal Fe dopant concentrations are, however, inconsistent, and the origin of the increased activity due to Fe dopants in mixed oxides has not been identified so far. Here, we combine density functional theory calculations, scanning tunneling microscopy, and OER activity measurements on atomically defined Fe-doped Co oxyhydroxide nanoparticles supported on a gold surface to establish the link between the activity and the Fe distribution and concentration within the oxyhydroxide phase. We find that addition of Fe results in distinct effects depending on its location on edge or basal plane sites of the oxyhydroxide nanoparticles, resulting in a nonlinear OER activity as a function of Fe content. Fe atom substitution itself does not lead to intrinsically more active OER sites than the best Co sites. Instead, the sensitivity to Fe promoter content is explained by the strong preference for Fe to locate on the most active edge sites of oxyhydroxide nanoparticles, which for low Fe concentrations stabilizes the particles but in higher concentrations leads to a shell structure with less active Fe on all edge positions. The optimal Fe content thereby becomes dependent on nanoparticle size. Our findings demonstrate that synthesis strategies that adjust not only the Fe concentration in mixed oxides but also its distribution within a catalyst nanoparticle can lead to enhanced OER performance.

Lateral Interfaces between Monolayer MoS2 Edges and Armchair Graphene Nanoribbons on Au(111).

The realization of electronic devices based on heterostructures of metallic, semiconducting, or insulating two-dimensional materials relies on the ability to form structurally coherent and clean interfaces between them, vertically or laterally. Lateral two-dimensional heterostructures that fuse together two different materials in a well-controlled manner have attracted recent attention, but the methods to form seamless interfaces between structurally dissimilar materials, such as graphene and transition-metal dichalcogenides (TMDCs), are still limited. Here, we investigate the structure of the lateral interfaces that arise between monolayer MoS2 flakes on Au(111) and two families of armchair graphene nanoribbons (GNRs) created through on-surface assisted Ullmann coupling using regular organobromine precursors for GNR synthesis. We find that parallel alignment between the GNR armchair edge and MoS2 leads to van der Waals bonded nanoribbons, whereas a perpendicular orientation is characterized by a single phenyl-group of the GNR covalently bonded to S on the edge. The edge-on bonding is facilitated by a hydrogen treatment of the MoS2, and temperature control during growth is shown to influence the nanoribbon width and the yield of covalently attached nanoribbons. Interestingly, the temperatures needed to drive the intramolecular dehydrogenation during GNR formation are lowered significantly by the presence of MoS2, which we attribute to enhanced hydrogen recombination at the MoS2 edges. These results are a demonstration of a viable method to make laterally bonded graphene nanostructures to TMDCs to be used in further investigations of two-dimensional heterostructure junctions.

Site-dependent reactivity of MoS2 nanoparticles in hydrodesulfurization of thiophene.

The catalytically active site for the removal of S from organosulfur compounds in catalytic hydrodesulfurization has been attributed to a generic site at an S-vacancy on the edge of MoS2 particles. However, steric constraints in adsorption and variations in S-coordination means that not all S-vacancy sites should be considered equally active. Here, we use a combination of atom-resolved scanning probe microscopy and density functional theory to reveal how the generation of S-vacancies within MoS2 nanoparticles and the subsequent adsorption of thiophene (C4H4S) depends strongly on the location on the edge of MoS2. Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS2 particle corners leads to an activated and concerted displacement of neighboring edge S. This mechanism allows the reactant to self-generate a double CUS site that reduces steric effects in more constrained sites along the edge.

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.

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.

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.

Visualizing hydrogen-induced reshaping and edge activation in MoS2 and Co-promoted MoS2 catalyst clusters.

Hydrodesulfurization catalysis ensures upgrading and purification of fossil fuels to comply with increasingly strict regulations on S emissions. The future shift toward more diverse and lower-quality crude oil supplies, high in S content, requires attention to improvements of the complex sulfided CoMo catalyst based on a fundamental understanding of its working principles. In this study, we use scanning tunneling microscopy to directly visualize and quantify how reducing conditions transforms both cluster shapes and edge terminations in MoS2 and promoted CoMoS-type hydrodesulfurization catalysts. The reduced catalyst clusters are shown to be terminated with a fractional coverage of sulfur, representative of the catalyst in its active state. By adsorption of a proton-accepting molecular marker, we can furthermore directly evidence the presence of catalytically relevant S-H groups on the Co-promoted edge. The experimentally observed cluster structure is predicted by theory to be identical to the structure present under catalytic working conditions.

Sulfur-driven switching of the Ullmann coupling on Au(111).

We demonstrate a method to selectively switch the Ullmann coupling reaction of 2,8-dibromodibenzothiophene on a Au(111) support. The Ullmann coupling reaction is effective already at low temperature, but the complete inhibition of the same reaction can be achieved on Au(111) pre-exposed to H2S. The marked difference in reactivity of pretreated Au(111) is explained by the S-passivation of free Au atoms emerging from reconstruction sites. The inhibited state can be fully lifted by removing the S via hydrogen gas post-exposure.

Phase Transitions of Cobalt Oxide Bilayers on Au(111) and Pt(111): The Role of Edge Sites and Substrate Interactions.

Well-characterized metal oxides supported on single crystal surfaces serve as valuable model systems to study fundamental chemical properties and reaction mechanisms in heterogeneous catalysis or as new thin film metal oxide catalysts in their own right. Here, we present scanning tunneling microscopy and X-ray photoelectron spectroscopy results for cobalt oxide nanoislands that reveal the detailed atomistic mechanisms leading to transitions between Co-O bilayer and O-Co-O trilayer, induced by oxidation in O2 and reductive vacuum annealing treatments, respectively. By comparing between two different noble metal substrates, Au(111) and Pt(111), we further address the influence of the substrate. Overall, nanoisland edges act to initiate both the oxidation and reduction processes on both substrates. However, important influences of the choice of substrate were found, as the progress of oxidation includes intermediate steps on Au(111) not observed on Pt(111), where the oxidation on the other hand takes place at a significantly higher rate. During reductive treatment of trilayer, the bilayer structure gradually reappears on Pt(111), but not on Au(111) where the reduction rather results in the appearance of a stacked cobalt oxide morphology. These observations point to strong differences in the catalytic behavior between Au and Pt supported cobalt oxides, despite the otherwise strong structural similarities.

Long-Range Orientational Self-Assembly, Spatially Controlled Deprotonation, and Off-Centered Metalation of an Expanded Porphyrin.

Expanded porphyrins are large-cavity macrocycles with enormous potential in coordination chemistry, anion sensing, photodynamic therapy, and optoelectronics. In the last two decades, the surface science community has assessed the physicochemical properties of tetrapyrrolic-like macrocycles. However, to date, the sublimation, self-assembly and atomistic insights of expanded porphyrins on surfaces have remained elusive. Here, we show the self-assembly on Au(111) of an expanded aza-porphyrin, namely, an "expanded hemiporphyrazine", through a unique growth mechanism based on long-range orientational self-assembly. Furthermore, a spatially controlled "writing" protocol on such self-assembled architecture is presented based on the STM tip-induced deprotonation of the inner protons of individual macrocycles. Finally, the capability of these surface-confined macrocycles to host lanthanide elements is assessed, introducing a novel off-centered coordination motif. The presented findings represent a milestone in the fields of porphyrinoid chemistry and surface science, revealing a great potential for novel surface patterning, opening new avenues for molecular level information storage, and boosting the emerging field of surface-confined coordination chemistry involving f-block elements.

Thermal selectivity of intermolecular versus intramolecular reactions on surfaces.

On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure.

Temperature-controlled metal/ligand stoichiometric ratio in Ag-TCNE coordination networks.

The deposition of tetracyanoethylene (TCNE) on Ag(111), both at Room Temperature (RT, 300 K) and low temperatures (150 K), leads to the formation of coordination networks involving silver adatoms, as revealed by Variable-Temperature Scanning Tunneling Microscopy. Our results indicate that TCNE molecules etch away material from the step edges and possibly also from the terraces, which facilitates the formation of the observed coordination networks. Moreover, such process is temperature dependent, which allows for different stoichiometric ratios between Ag and TCNE just by adjusting the deposition temperature. X-ray Photoelectron Spectroscopy and Density Functional Theory calculations reveal that charge-transfer from the surface to the molecule and the concomitant geometrical distortions at both sides of the organic/inorganic interface might facilitate the extraction of silver atoms from the step-edges and, thus, its incorporation into the observed TCNE coordination networks.

Charge transfer-assisted self-limited decyanation reaction of TCNQ-type electron acceptors on Cu(100).

TCNQ derivatives adsorbed on a metal surface undergo a self-limited decyanation reaction that only affects two out of the four cyano groups in the molecule. Combined Scanning Tunneling Microscopy/X-ray Photoelectron Spectroscopy experiments and Density Functional Theory calculations relate the self-limiting behavior to the transfer of electrons from the metal to the molecule.

Formation of a surface covalent organic framework based on polyester condensation.

The reaction between 1,3,5-tris(4-hydroxyphenyl)benzene and benzene-1,3,5-tricarbonyl trichloride leads to polyester condensation and formation of a novel COF on an Au(111) surface. The characterization performed in situ by means of variable temperature STM and XPS reveals the formation of an array of hexagonal cavities with ca. 2 nm size.

Formation of self-assembled chains of tetrathiafulvalene on a Cu(100) surface.

Formation of self-assembled chains of tetrathiafulvalene (TTF) on the Cu(100) surface has been investigated by scanning tunneling microscopy and density functional theory calculations that include semiempirical van der Waals (vdW) interaction corrections. The calculations show that the chain structures observed in the experiments can only be explained by including the vdW interactions. The molecules are tilted along the chain in order to achieve maximal intermolecular interaction. The chains are metastable on the surface, which is consistent with the experimental observation that they disappear after annealing. The fact that all TTF chains observed in the experiment are short might be possibly explained by the interplay between the stabilizing vdW molecule-molecule interaction and the destabilizing rearrangement of surface atoms due to the strong molecule-substrate interaction.