h-BN in the making: The surface chemistry of borazine on Rh(111).

Borazine is a well-established precursor molecule for the growth of hexagonal boron nitride (h-BN) via chemical vapor deposition on metal substrates. To understand the formation of the h-BN/Rh(111) moiré from borazine on a molecular level, we investigated the low-temperature adsorption and thermally induced on-surface reaction of borazine on Rh(111) in situ using synchrotron radiation-based high-resolution x-ray photoelectron spectroscopy (XPS), temperature-programmed XPS, and near-edge x-ray absorption fine structure measurements. We find that borazine adsorbs mainly as an intact molecule and have identified a flat-lying adsorption geometry. Borazine multilayers are observed to desorb below 200 K. Starting at about 300 K, dehydrogenation of the remaining borazine and borazine fragments takes place, and disordered boron nitride starts to grow. Above 600 K, the formation of the h-BN sets in. Finally, at 1100 K, the conversion to h-BN is complete. The h-BN formed by deposition and post-annealing was compared to the h-BN grown by an established procedure, proving the successful preparation of the desired two-dimensional material.

Impact of Catalysis-Relevant Oxidation and Annealing Treatments on Nanostructured GaRh Alloys.

In this study, we examine the surface-derived electronic and chemical structures of nanostructured GaRh alloys as a model system for supported catalytically active liquid metal solutions (SCALMS), a novel catalyst candidate for dehydrogenation reactions that are important for the petrochemical and hydrogen energy industry. It is reported that under ambient conditions, SCALMS tends to form a gallium oxide shell, which can be removed by an activation treatment at elevated temperatures and hydrogen flow to enhance the catalytic reactivity. We prepared a 7 at. % Rh containing the GaRh sample and interrogated the evolution of the surface chemical and electronic structure by photoelectron spectroscopy (complemented by scanning electron microscopy) upon performing surface oxidation and (activation treatment mimicking) annealing treatments in ultrahigh vacuum conditions. The initially pronounced Rh 4d and Fermi level-derived states in the valence band spectra disappear upon oxidation (due to formation of a GaOx shell) but reemerge upon annealing, especially for temperatures of 600 °C and above, i.e., when the GaOx shell is efficiently being removed and the Ga matrix is expected to be liquid. At the same temperature, new spectroscopic features at both the high and low binding energy sides of the Rh 3d5/2 spectra are observed, which we attribute to new GaRh species with depleted and enriched Rh contents, respectively. A liquefied and GaOx-free surface is also expected for GaRh SCALMS at reaction conditions, and thus the revealed high-temperature properties of the GaRh alloy provide insights about respective catalysts at work.

The Norbornadiene/Quadricyclane Pair as Molecular Solar Thermal Energy Storage System: Surface Science Investigations.

For the transition to renewable energy sources, novel energy storage materials are more important than ever. This review addresses so-called molecular solar thermal (MOST) systems, which appear very promising since they combine light harvesting and energy storing in one-photon one-molecule processes. The focus is on norbornadiene (NBD), a particularly interesting candidate, which is converted to the strained valence isomer quadricyclane (QC) upon irradiation. The stored energy can be released on demand. The energy-releasing cycloreversion from QC to NBD can be initiated by a thermal, catalytic, or electrochemical trigger. The reversibility of the energy storage and release cycles determines the general practicality of a MOST system. In the search for derivatives, which enable large-scale applications, fundamental surface science studies help to assess the feasibility of potential substituted NBD/QC couples. We include investigations under well-defined ultra-high vacuum (UHV) conditions as well as experiments in liquid phase. Next to the influence of the catalytically active surfaces on the isomerization between the two valence isomers, information on adsorption geometries, thermal stability limits, and reaction pathways of the respective molecules are discussed. Moreover, laboratory-scaled test devices demonstrate the proof of concept in various areas of application.

Bromination of 2D materials.

The adsorption, reaction and thermal stability of bromine on Rh(111)-supported hexagonal boron nitride (h-BN) and graphene were investigated. Synchrotron radiation-based high-resolution x-ray photoelectron spectroscopy (XPS) and temperature-programmed XPS allowed us to follow the adsorption process and the thermal evolutionin situon the molecular scale. Onh-BN/Rh(111), bromine adsorbs exclusively in the pores of the nanomesh while we observe no such selectivity for graphene/Rh(111). Upon heating, bromine undergoes an on-surface reaction onh-BN to form polybromides (170-240 K), which subsequently decompose to bromide (240-640 K). The high thermal stability of Br/h-BN/Rh(111) suggests strong/covalent bonding. Bromine on graphene/Rh(111), on the other hand, reveals no distinct reactivity except for intercalation of small amounts of bromine underneath the 2D layer at high temperatures. In both cases, adsorption is reversible upon heating. Our experiments are supported by a comprehensive theoretical study. DFT calculations were used to describe the nature of theh-BN nanomesh and the graphene moiré in detail and to study the adsorption energetics and substrate interaction of bromine. In addition, the adsorption of bromine onh-BN/Rh(111) was simulated by molecular dynamics using a machine-learning force field.

Poly(benzimidazobenzophenanthroline)-Ladder-Type Two-Dimensional Conjugated Covalent Organic Framework for Fast Proton Storage.

Electrochemical proton storage plays an essential role in designing next-generation high-rate energy storage devices, e.g., aqueous batteries. Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are promising electrode materials, but their competitive proton and metal-ion insertion mechanisms remain elusive, and proton storage in COFs is rarely explored. Here, we report a perinone-based poly(benzimidazobenzophenanthroline) (BBL)-ladder-type 2D c-COF for fast proton storage in both a mild aqueous Zn-ion electrolyte and strong acid. We unveil that the discharged C-O- groups exhibit largely reduced basicity due to the considerable π-delocalization in perinone, thus affording the 2D c-COF a unique affinity for protons with fast kinetics. As a consequence, the 2D c-COF electrode presents an outstanding rate capability of up to 200 A g-1 (over 2500 C), surpassing the state-of-the-art conjugated polymers, COFs, and metal-organic frameworks. Our work reports the first example of pure proton storage among COFs and highlights the great potential of BBL-ladder-type 2D conjugated polymers in future energy devices.

Surface science and liquid phase investigations of oxanorbornadiene/oxaquadricyclane ester derivatives as molecular solar thermal energy storage systems on Pt(111).

The transition to renewable energy sources comes along with the search for new energy storage solutions. Molecular solar thermal systems directly harvest and store solar energy in a chemical manner. By a suitable molecular design, a higher overall efficiency can be achieved. In this study, we investigate the surface chemistry of oxa-norbornadiene/quadricyclane derivatives on a Pt(111) surface. Specifically, we focus on the energy storage and release properties of molecules that are substituted with ester moieties of different sizes. For our model catalytic approach, synchrotron radiation-based x-ray photoelectron spectroscopy measurements were conducted in ultra-high vacuum (UHV) and correlated with the catalytic behavior in the liquid phase monitored by photochemical infrared reflection absorption spectroscopy. The differences in their spectral appearance enabled us to unambiguously differentiate the energy-lean and energy-rich isomers and decomposition products. Next to qualitative information on the adsorption motifs, temperature-programmed experiments allowed for the observation of thermally induced reactions and the deduction of the related reaction pathways. We analyzed the selectivity of the cycloreversion reaction from the energy-rich quadricyclane derivative to its energy-lean norbornadiene isomer and competing processes, such as desorption and decomposition. For the 2,3-bis(methylester)-substitution, the cycloreversion reaction was found to occur between 310 and 340 K, while the thermal stability limit of the compounds was determined to be 380 K. The larger 2,3-bis(benzylester) derivatives have a lower apparent adsorption energy and a decomposition onset already at 135 K. In the liquid phase (in acetonitrile), we determined the rate constants for the cycloreversion reaction on Pt(111) to k = 5.3 × 10-4 s-1 for the 2,3-bis(methylester)-substitution and k = 6.3 × 10-4 s-1 for the 2,3-bis(benzylester) derivative. The selectivities were of >99% and 98% for the two molecules, respectively. The difference in the catalytic behavior of Pt(111) for both derivatives is less pronounced in the liquid phase than in UHV, which we attribute to the passivation of the Pt(111) surface by carbonaceous species under ambient conditions.

Bromine Adsorption and Thermal Stability on Rh(111): A Combined XPS, LEED and DFT Study.

This study addresses a fundamental question in surface science: the adsorption of halogens on metal surfaces. Using synchrotron radiation-based high-resolution X-ray photoelectron spectroscopy (XPS), temperature-programmed XPS, low-energy electron diffraction (LEED) and density functional theory (DFT) calculations, we investigated the adsorption and thermal stability of bromine on Rh(111) in detail. The adsorption of elemental bromine on Rh(111) at 170 K was followed in situ by XPS in the Br 3d region, revealing two individual, coverage-dependent species, which we assign to fcc hollow- and bridge-bound atomic bromine. In addition, we find a significant shift in binding energy upon increasing coverage due to adsorbate-adsorbate interactions. Subsequent heating shows a high thermal stability of bromine on Rh(111) up to above 1000 K, indicating strong covalent bonding. To complement the XPS data, LEED was used to study the long-range order of bromine on Rh(111): we observe a (√3×√3)R30° structure for low coverages (≤0.33 ML) and a star-shaped compression structure for higher coverages (0.33-0.43 ML). Combining LEED and DFT calculations, we were able to visualize bromine adsorption on Rh(111) in real space for varying coverages.

Isolated Rh atoms in dehydrogenation catalysis.

Isolated active sites have great potential to be highly efficient and stable in heterogeneous catalysis, while enabling low costs due to the low transition metal content. Herein, we present results on the synthesis, first catalytic trials, and characterization of the Ga9Rh2 phase and the hitherto not-studied Ga3Rh phase. We used XRD and TEM for structural characterization, and with XPS, EDX we accessed the chemical composition and electronic structure of the intermetallic compounds. In combination with catalytic tests of these phases in the challenging propane dehydrogenation and by DFT calculations, we obtain a comprehensive picture of these novel catalyst materials. Their specific crystallographic structure leads to isolated Rhodium sites, which is proposed to be the decisive factor for the catalytic properties of the systems.

Preparation of geometrically highly controlled Ga particle arrays on quasi-planar nanostructured surfaces as a SCALMS model system.

This study establishes a preparative route towards a model system for supported catalytically active liquid metal solutions (SCALMS) on nanostructured substrates. This model is characterized by a uniquely precise geometrical control of the gallium particle size distribution. In a SCALMS system, the Ga serves as a matrix material which can be decorated with a catalytically active material subsequently. The corresponding Ga containing precursor is spin-coated on aluminum based substrates, previously nanostructured by electrochemical anodization. The highly ordered substrates are functionalized with distinct oxide coatings by atomic layer deposition (ALD) independently from the morphology. After preparation of the metal particles on the oxide interface, the characterization of our model system in terms of its geometry parameters (droplet diameter, size distribution and population density) points to SiO2 as the best suited surface for a highly controlled geometry. This flexible model system can be functionalized with a dissolved noble metal catalyst for the application chosen.

Surface Studies on the Energy Release of the MOST System 2-Carbethoxy-3-Phenyl-Norbornadiene/Quadricyclane (PENBD/PEQC) on Pt(111) and Ni(111).

Novel energy-storage solutions are necessary for the transition from fossil to renewable energy sources. Auspicious candidates are so-called molecular solar thermal (MOST) systems. In our study, we investigate the surface chemistry of a derivatized norbornadiene/quadricyclane molecule pair. By using suitable push-pull substituents, a bathochromic shift of the absorption onset is achieved, allowing a greater overlap with the solar spectrum. Specifically, the adsorption and thermally induced reactions of 2-carbethoxy-3-phenyl-norbornadiene/quadricyclane are assessed on Pt(111) and Ni(111) as model catalyst surfaces by synchrotron radiation-based X-ray photoelectron spectroscopy (XPS). Comparison of the respective XP spectra enables the distinction of the energy-rich molecule from its energy-lean counterpart and allows qualitative information on the adsorption motifs to be derived. Monitoring the quantitative cycloreversion between 140 and 230 K spectroscopically demonstrates the release of the stored energy to be successfully triggered on Pt(111). Heating to above 300 K leads to fragmentation of the molecular framework. On Ni(111), no conversion of the energy-rich compound takes place. The individual decomposition pathways of the two isomers begin at 160 and 180 K, respectively. Pronounced desorption of almost the entire surface coverage only occurs for the energy-lean molecule on Ni(111) above 280 K; this suggests weakly bound species. The correlation between adsorption motif and desorption behavior is important for applications of MOST systems in heterogeneously catalyzed processes.

Insertions and deletions in the hypervariable region of the hepatitis E virus genome in individuals with acute and chronic infection.

BACKGROUND AND AIMS: Hepatitis E virus is a major cause of acute hepatitis worldwide and can progress to chronicity in immunocompromised individuals. Various virus-host recombination events have been reported in the hypervariable region of the hepatitis E virus genome, but the patterns of assembly and selection remain unclear. METHODS: To gain further insight into viral evolution, we assessed the presence of low abundance variants in 16 samples from individuals with acute or chronic infection using a targeted next-generation sequencing approach. RESULTS: In seven samples, different variants with insertions and/or deletions were identified. Among them, eight insertions originating either from human genes or from the hepatitis E virus genome. Five different deletions could be identified. The amino acid composition of sequences with insertions showed a higher frequency of lysine and a lower abundance of proline, and additionally acetylation and ubiquitination sites were more frequent than in hepatitis E virus wild-type sequences. CONCLUSIONS: These findings suggest that the nucleotide composition of insertions and sites for post-translational modification may contribute to recombination events. Although the impact of low-level hepatitis E virus variants is uncertain, our results highlight the importance of a highly sensitive next-generation sequencing approach to capture the full diversity of hypervariable region.

Surface Chemistry of the Molecular Solar Thermal Energy Storage System 2,3-Dicyano-Norbornadiene/Quadricyclane on Ni(111).

The front cover artwork is provided by the group of Prof. Dr. Christian Papp at Physical Chemistry II of FAU Erlangen-Nürnberg and FU Berlin. The image shows the isomerization reaction of the molecule pair 2,3-dicyano-norbornadiene/quadricyclane as potential molecular solar thermal (MOST) energy storage system. Read the full text of the Research Article at 10.1002/cphc.202200199.

Molecular Stacking on Graphene.

The sequential vertical polyfunctionalization of 2D addend-patterned graphene is still elusive. Here, we report a practical realization of this goal via a "molecular building blocks" approach, which is based on a combination of a lithography-assisted reductive functionalization approach and a post-functionalization step to sequentially and controllably link the molecular building blocks ethylpyridine, cis-dichlorobis(2,2'-bipyridyl)ruthenium, and triphenylphosphine (4-methylbenzenethiol, respectively) on selected lattice regions of a graphene matrix. The assembled 2D hetero-architectures are unambiguously characterized by various spectroscopic and microscopic measurements, revealing the stepwise stacking of the molecular building blocks on the graphene surface. Our method overcomes the current limitation of a one-layer-only binding to the graphene surface and opens the door for a vertical growth in the z-direction.

Surface Chemistry of the Molecular Solar Thermal Energy Storage System 2,3-Dicyano-Norbornadiene/Quadricyclane on Ni(111).

Molecular solar thermal (MOST) systems are a promising approach for the introduction of sustainable energy storage solutions. We investigated the feasibility of the dicyano-substituted norbornadiene/quadricyclane molecule pair on Ni(111) for catalytic model studies. This derivatization is known to lead to a desired bathochromic shift of the absorption maximum of the parent compound. In our experiments further favorable properties were found: At low temperatures, both molecules adsorb intact without any dissociation. In situ temperature-programmed HR-XPS experiments reveal the conversion of (CN)2 -quadricyclane to (CN)2 -norbornadiene under energy release between 175 and 260 K. The absence of other surface species due to side reactions indicates full isomerization. Further heating leads to the decomposition of the molecular framework into smaller carbonaceous fragments above 290 K and finally to amorphous structures, carbide and nitride above 400 K. DFT calculations gave insights into the adsorption geometries. (CN)2 -norbornadiene is expected to interact stronger with the surface, with flat configurations being favorable. (CN)2 -quadricyclane exhibits smaller adsorption energies with negligible differences for flat and side-on geometries. Simulated XP spectra are in good agreement with experimental findings further supporting the specific spectroscopic fingerprints for both valence isomers.

Reactivity and Passivation of Fe Nanoclusters on h-BN/Rh(111).

The reactivity of iron nanocluster arrays on h-BN/Rh(111) was studied using in situ high-resolution X-ray photoelectron spectroscopy. The morphology and reactivity of the iron nanoclusters (Fe-NCs) were investigated by CO adsorption. On-top and hollow/edge sites were determined to be the available adsorption sites on the as-prepared Fe-NCs and CO dissociation was observed at 300 K. C- and O-precovered Fe-NCs showed no catalytic activity towards CO dissociation because the hollow/edge sites were blocked by the C and O atoms. Therefore, these adsorption sites were identified to be the most active sites of the Fe-NCs.

Selective Oxygen and Hydrogen Functionalization of the h-BN/Rh(111) Nanomesh.

We present detailed studies on the covalent adsorption of molecular oxygen and atomic hydrogen on the hexagonal boron nitride (h-BN) nanomesh on Rh(111). The functionalization of this two-dimensional (2D) material was investigated under ultra-high vacuum conditions using synchrotron radiation-based in situ high-resolution X-ray photoelectron spectroscopy, temperature-programmed X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. We are able to provide a deep insight into the adsorption behavior and thermal stability of oxygen and hydrogen on h-BN/Rh(111). Oxygen functionalization was achieved via a supersonic molecular beam while hydrogen functionalization was realized using an atomic hydrogen source. Adsorption of the respective species was observed to occur selectively in the pores of h-BN leading to spatially defined modification of the 2D layer. The adsorption of the observed molecular oxygen species was found to be an activated process that requires high-energy oxygen molecules. Upon heating to 700 K, oxygen functionalization was observed to be almost reversible except for small amounts of boron oxides evolving due to the reaction of oxygen with the 2D material. Hydrogen functionalization of h-BN/Rh(111) was fully reversed upon heating to about 640 K.

Surface oxidation-induced restructuring of liquid Pd-Ga SCALMS model catalysts.

We have examined model systems for the recently reported Pd-Ga Supported Catalytically Active Liquid Metal Solutions (SCALMS) catalysts using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) under oxidizing conditions. Gallium is known to be highly prone to oxidation and in practical applications, handling of the catalyst material in air or the presence of traces of oxygen in the reactor are unavoidable. Therefore, we expect our results to be of high relevance for the application of Ga-based SCALMS catalysts. Pd-Ga alloy samples of 1.3 and 1.8 at% Pd content were exposed to molecular oxygen at different pressures between 3 × 10-7 and 1 mbar and a temperature of 550 K. We observe the formation of wetting Ga2O3 films upon exposure to molecular oxygen. The absolute thicknesses of the oxide films depend on oxygen pressure, with values ranging from ∼12 Å at 10-7 to 10-5 mbar to ∼50 Å at 1 mbar. The formed metal-oxide interface leads to a redistribution of Pd, which accumulates at the boundary between the wetting oxide film and the metal substrate as a response to the oxide film growth. A maximum Pd 3d intensity is observed at an oxide thickness of 5 Å. For thicker films, the Pd 3d signal and the Ga 3d signal ascribed to the metallic substrate decrease in parallel, which is attributed to the oxide layer growing on top of the liquid metal alloy. From this observation, we conclude that no significant amount of Pd is bound in the newly formed oxide film. Density-functional theory (DFT) calculations support the experimental observations.

Oxidation induced restructuring of Rh-Ga SCALMS model catalyst systems.

Supported catalytically active liquid metal solutions have been receiving increasing attention recently. We investigated the oxidation behavior of macroscopic Rh-Ga alloy droplets and Rh-Ga model catalyst nanoparticles supported on SiO2/Si(100) with low Rh content (<2.5 at. %) by x-ray photoelectron spectroscopy in ultra-high vacuum and under near-ambient pressure conditions using different photon energies and also using transmission electron microscopy. The experiments are accompanied by computational studies on the Ga oxide/Rh-Ga interface and Rh-Ga intermetallic compounds. For both Rh-Ga alloy droplets and Rh-Ga model catalyst nanoparticles, exposure to molecular oxygen leads to the formation of an oxide shell in which Rh is enriched. Transmission electron microscopy on the Rh-Ga nanoparticles confirms the formation of an ∼4 nm thick gallium oxide film containing Rh. Based on ab initio molecular dynamics and computational studies on the Ga2O3/Ga interface, it is concluded that Rh incorporation into the Ga2O3 film occurs by substituting octahedrally coordinated Ga.

Ethylene: Its adsorption, reaction, and coking on Pt/h-BN/Rh(111) nanocluster arrays.

We present well-ordered Pt nanocluster arrays supported on the h-BN/Rh(111) Moiré as a model system for an ethylene dehydrogenation catalyst. Thereby, the h-BN nanomesh serves as a chemically inert eggbox-like template for clusters with a narrow size distribution. The thermal evolution of ethylene is investigated by synchrotron-based high-resolution in situ x-ray photoelectron spectroscopy on the Pt nanoclusters. We compare our results with data on Pt(111) and Pt(355). Interestingly, the Pt nanoclusters and Pt(355) behave very similarly. Both open a new reaction pathway via vinylidene in addition to the route via ethylidyne known for Pt(111). Due to the importance of coking in ethylene dehydrogenation on Pt catalysts, we also studied C2H4 adsorption and decomposition on carbon precovered Pt nanoclusters. While the amount of adsorbed ethylene decreases linearly with the carbon coverage, we found that edge sites are more affected than facet sites and that the vinylidene reaction pathway is effectively suppressed by carbon residues.