Starting from a single layer of NbS grown on graphene by molecular beam epitaxy, the single unit cell thick 2D materials NbS-2D and NbS-2D are created using two different pathways. Either annealing under sulfur-deficient conditions at progressively higher temperatures or deposition of increasing amounts of Nb at elevated temperature result in phase-pure NbS-2D followed by NbS-2D. The materials are characterized by scanning tunneling microscopy, scanning tunneling spectroscopy, and X-ray photoemission spectroscopy.
View Article and Find Full Text PDFTwo ultimately thin vanadium-rich 2D materials based on VS are created via molecular beam epitaxy and investigated using scanning tunneling microscopy, X-ray photoemission spectroscopy, and density functional theory (DFT) calculations. The controlled synthesis of stoichiometric single-layer VS or either of the two vanadium-rich materials is achieved by varying the sample coverage and sulfur pressure during annealing. Through annealing of small stoichiometric single-layer VS islands without S pressure, S-vacancies spontaneously order in 1D arrays, giving rise to patterned adsorption.
View Article and Find Full Text PDFReaction products in heterogeneous catalysis can be detected either on the catalyst surface or in the gas phase after desorption. However, if atoms are dissolved in the catalyst bulk, then reaction channels can become hidden. This is the case if the dissolution rate of the deposits is faster than their formation rate.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
August 2022
Hydrogenated graphene (H-Gr) is an extensively studied system not only because of its capabilities as a simplified model system for hydrocarbon chemistry but also because hydrogenation is a compelling method for Gr functionalization. However, knowledge of how H-Gr interacts with molecules at higher pressures and ambient conditions is lacking. Here we present experimental and theoretical evidence that room temperature O exposure at millibar pressures leads to preferential removal of H dimers on H-functionalized graphene, leaving H clusters on the surface.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
March 2022
Room temperature oxygen hydrogenation below graphene flakes supported by Ir(111) is investigated through a combination of X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory calculations using an evolutionary search algorithm. We demonstrate how the graphene cover and its doping level can be used to trap and characterize dense mixed O-OH-HO phases that otherwise would not exist. Our study of these graphene-stabilized phases and their response to oxygen or hydrogen exposure reveals that additional oxygen can be dissolved into them at room temperature creating mixed O-OH-HO phases with an increased areal coverage underneath graphene.
View Article and Find Full Text PDFHeterogeneous catalyst surfaces are dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts' action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the timescales of the dynamic changes. Here we use the CO oxidation reaction and a Pd(100) model catalyst to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy.
View Article and Find Full Text PDFA setup capable of conducting gas pulse-X-ray probe ambient pressure photoelectron spectroscopy with high time resolution is presented. The setup makes use of a fast valve that creates gas pulses with an internal pressure in the mbar range and a rising edge of few hundreds of microseconds. A gated detector based on a fast camera is synchronized with the valve operation to measure X-ray photoemission spectra with up to 20 μs time resolution.
View Article and Find Full Text PDFThe SPECIES beamline has been transferred to the new 1.5 GeV storage ring at the MAX IV Laboratory. Several improvements have been made to the beamline and its endstations during the transfer.
View Article and Find Full Text PDFCluster superlattice membranes consist of a two-dimensional hexagonal lattice of similar-sized nanoclusters sandwiched between single-crystal graphene and an amorphous carbon matrix. The fabrication process involves three main steps, the templated self-organization of a metal cluster superlattice on epitaxial graphene on Ir(111), conformal embedding in an amorphous carbon matrix, and subsequent lift-off from the Ir(111) substrate. The mechanical stability provided by the carbon-graphene matrix makes the membrane stable as a free-standing material and enables transfer to other substrates.
View Article and Find Full Text PDFIn this topical review we catagorise all ambient pressure x-ray photoelectron spectroscopy publications that have appeared between the 1970s and the end of 2018 according to their scientific field. We find that catalysis, surface science and materials science are predominant, while, for example, electrocatalysis and thin film growth are emerging. All catalysis publications that we could identify are cited, and selected case stories with increasing complexity in terms of surface structure or chemical reaction are discussed.
View Article and Find Full Text PDFIn the production of 2 generation ethanol, using Saccharomyces cerevisiae, the highest productivity obtained using C5/C6 fermenting yeast is in the co-fermentation phase, in which xylose and glucose are fermented simultaneously. Extending this phase in a fed-batch process increases the yield, rate and additionally reduces needed yeast amount for pitching. Extending this phase, as long as possible, would further enhance yield and economy of the process.
View Article and Find Full Text PDFWith the introduction of the multi-bend achromats in the new fourth-generation storage rings the emittance has decreased by an order of magnitude resulting in increased brightness. However, the higher brightness comes with smaller beam sizes and narrower radiation cones. As a consequence, the requirements on mechanical stability regarding the beamline components increases.
View Article and Find Full Text PDFAtomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy.
View Article and Find Full Text PDFHydrogen functionalization of graphene by exposure to vibrationally excited H molecules is investigated by combined scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, X-ray photoelectron spectroscopy measurements, and density functional theory calculations. The measurements reveal that vibrationally excited H molecules dissociatively adsorb on graphene on Ir(111) resulting in nanopatterned hydrogen functionalization structures. Calculations demonstrate that the presence of the Ir surface below the graphene lowers the H dissociative adsorption barrier and allows for the adsorption reaction at energies well below the dissociation threshold of the H-H bond.
View Article and Find Full Text PDFThe interaction of CO with the FeO(001)-(√2 × √2)R45° surface was studied using temperature-programmed desorption (TPD), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS), the latter both under ultrahigh vacuum (UHV) conditions and in CO pressures up to 1 mbar. In general, the CO-FeO interaction is found to be weak. The strongest adsorption occurs at surface defects, leading to small TPD peaks at 115, 130, and 190 K.
View Article and Find Full Text PDFOur scanning tunneling microscopy and X-ray photoelectron spectroscopy experiments along with first-principles calculations uncover the rich phenomenology and enable a coherent understanding of carbon vapor interaction with graphene on Ir(111). At high temperatures, carbon vapor not only permeates to the metal surface but also densifies the graphene cover. Thereby, in addition to underlayer graphene growth, upon cool down also severe wrinkling of the densified graphene cover is observed.
View Article and Find Full Text PDFAppl Microbiol Biotechnol
June 2017
The production of natural aroma compounds is an expanding field within the branch of white biotechnology. Three aromatic compounds of interest are cinnamaldehyde, the typical cinnamon aroma that has applications in agriculture and medical sciences, as well as cinnamyl alcohol and hydrocinnamyl alcohol, which have applications in the cosmetic industry. Current production methods, which rely on extraction from plant materials or chemical synthesis, are associated with drawbacks regarding scalability, production time, and environmental impact.
View Article and Find Full Text PDFBand gap engineering in hydrogen functionalized graphene is demonstrated by changing the symmetry of the functionalization structures. Small differences in hydrogen adsorbate binding energies on graphene on Ir(111) allow tailoring of highly periodic functionalization structures favoring one distinct region of the moiré supercell. Scanning tunneling microscopy and X-ray photoelectron spectroscopy measurements show that a highly periodic hydrogen functionalized graphene sheet can thus be prepared by controlling the sample temperature (T) during hydrogen functionalization.
View Article and Find Full Text PDFSPECIES is an undulator-based soft X-ray beamline that replaced the old I511 beamline at the MAX II storage ring. SPECIES is aimed at high-resolution ambient-pressure X-ray photoelectron spectroscopy (APXPS), near-edge X-ray absorption fine-structure (NEXAFS), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) experiments. The beamline has two branches that use a common elliptically polarizing undulator and monochromator.
View Article and Find Full Text PDFWe have examined the geometric and electronic structures of iron phthalocyanine assemblies on a Cu(111) surface at different sub- to mono-layer coverages and the changes induced by thermal annealing at temperatures between 250 and 320 °C by scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy. The symmetry breaking observed in scanning tunneling microscopy images is found to be coverage dependent and to persist upon annealing. Further, we find that annealing to temperatures between 300 and 320 °C leads to both desorption of iron phthalocyanine molecules from the surface and their agglomeration.
View Article and Find Full Text PDFBackground: Saccharomyces cerevisiae can be engineered to perform a multitude of different chemical reactions that are not programmed in its original genetic code. It has a large potential to function as whole-cell biocatalyst for one-pot multistep synthesis of various organic molecules, and it may thus serve as a powerful alternative or complement to traditional organic synthetic routes for new chemical entities (NCEs). However, although the selectivity in many cases is high, the catalytic activity is often low which results in low space-time-yields.
View Article and Find Full Text PDFA control point for keeping redox homeostasis in during fermentative growth is the dynamic regulation of transcription for the glycerol-3-phosphate dehydrogenase 2 () gene. In this study, the possibility to steer the activity of the promoter was investigated by placing it in strains with different ability to reoxidise NADH, and applying different environmental conditions. Flow cytometric analysis of reporter strains expressing green fluorescent protein () under the control of the promoter was used to determine the promoter activity at the single-cell level When placed in a strain background, the promoter displayed a 2-fold higher activity as compared to the strong constitutive glyceraldehyde-3-phosphate dehydrogenase ().
View Article and Find Full Text PDFLayered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic "water splitting" reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect of gold contact are only understood on a rudimentary level, which at present prevents further exploration. We have synthesized a model system of flat, layered cobalt oxide nanoislands supported on a single crystal gold (111) substrate.
View Article and Find Full Text PDFThe 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.
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