| 1. |
- Guimond, S., et al.
(författare)
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Vanadium oxide surfaces and supported vanadium oxide nanoparticles
- 2006
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Ingår i: Topics in catalysis. - : Springer Science and Business Media LLC. - 1022-5528 .- 1572-9028. ; 38:1-3, s. 117-125
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Tidskriftsartikel (refereegranskat)abstract
- The information obtained from the characterization of vanadium oxide single crystal surfaces is related to the study of vanadia nanoparticles supported on silica and alumina thin films, model systems for the so-called “supported monolayer vanadia catalysts”. It is found that these particles have properties similar to V2O3 surfaces, where the topmost V ions are involved in vanadyl groups and have a 5+ oxidation state. A vibrational spectroscopy investigation combined with DFT calculations show that the accepted interpretation of vibrational spectra from vanadia catalysts must be revised.
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| 2. |
- Lu, J. -L, et al.
(författare)
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Formation of one-dimensional crystalline silica on a metal substrate
- 2006
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 600:13, s. L164-L168
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Tidskriftsartikel (refereegranskat)abstract
- We have observed formation of one-dimensional silica structures of 0.5 nm in width on Mo(112) single crystal surface. Combination of high-resolution scanning tunneling microscopy, photoelectron and infrared spectroscopy, and density functional theory provides strong evidence for formation of paired rows of corner sharing [SiO4] tetrahedra chemisorbed on a metal substrate.
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| 3. |
- Todorova, T. K., et al.
(författare)
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Atomic structure of a thin silica film on a Mo(112) substrate : A combined experimental and theoretical study (vol 73, pg 165414, 2006)
- 2006
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 73:16
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Tidskriftsartikel (refereegranskat)abstract
- The atomic structure of the thin SiO2 film on a Mo(112) substrate has been determined based on a combination of density functional theory calculations and high-quality experimental data obtained from scanning tunneling microscopy, infrared reflection absorption spectroscopy, and x-ray photoelectron spectroscopy. The film consists of a honeycomblike, two-dimensional network of corner-sharing [SiO4] tetrahedra. One oxygen atom of each tetrahedron binds to the Mo(112) substrate and is located in a bridge position between Mo atoms located in rows protruding from the metal surface. The other three oxygen atoms form Si-O-Si bonds with the neighboring tetrahedra.
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| 4. |
- Todorova, T K, et al.
(författare)
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Atomic structure of a thin silica film on a Mo(112) substrate : A combined experimental and theoretical study
- 2006
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 73:16, s. 165414-
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Tidskriftsartikel (refereegranskat)abstract
- The atomic structure of the thin SiO2 film on a Mo(112) substrate has been determined based on a combination of density functional theory calculations and high-quality experimental data obtained from scanning tunneling microscopy, infrared reflection absorption spectroscopy, and x-ray photoelectron spectroscopy. The film consists of a honeycomblike, two-dimensional network of corner-sharing [SiO4] tetrahedra. One oxygen atom of each tetrahedron binds to the Mo(112) substrate and is located in a bridge position between Mo atoms located in rows protruding from the metal surface. The other three oxygen atoms form Si-O-Si bonds with the neighboring tetrahedra.
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| 5. |
- Weissenrieder, Jonas, et al.
(författare)
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Atomic structure of a thin silica film on a Mo(112) substrate : A two-dimensional network of SiO4 tetrahedra
- 2005
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 95:7, s. 1-4
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Tidskriftsartikel (refereegranskat)abstract
- The structure of a thin single crystalline SiO2 film grown on Mo(112) has been studied by scanning tunneling microscopy, infrared reflection absorption spectroscopy, and x-ray photoelectron spectroscopy. In excellent agreement with the experimental results, density functional theory calculations show that the film consists of a two-dimensional network of corner sharing [SiO4] tetrahedra, with one oxygen of each tetrahedron binding to the protruding Mo atoms of the Mo(112) surface.
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| 6. |
- Lu, J. -L, et al.
(författare)
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Low temperature CO induced growth of Pd supported on a monolayer silica film
- 2006
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 600:12, s. L153-L157
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Tidskriftsartikel (refereegranskat)abstract
- Nucleation, growth and sintering of Pd deposited on an ultra-thin silica film were studied by scanning tunneling microscopy and infrared reflection absorption spectroscopy. No preferential nucleation of Pd on the silica surface was observed both at 90 and 300 K deposition. When adsorbed on Pd clusters formed at 90 K, CO causes a strong sintering effect even at this temperature. The results are rationalized on the basis of a high mobility of Pd carbonyl-like species on the silica film. At a given Pd coverage, the extent of CO induced sintering cannot be achieved by annealing in vacuum. In addition, vacuum sintering, which commences above 700 K, goes simultaneously with interdiffusion of Pd and support.
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| 7. |
- Lu, J. -L., et al.
(författare)
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Structure, thermal stability, and CO adsorption properties of Pd nanoparticles supported on an ultra-thin SiO2 film
- 2007
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Ingår i: Surface review and letters. - 0218-625X. ; 14:5, s. 927-934
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Tidskriftsartikel (refereegranskat)abstract
- Nucleation, growth, and thermal stability of Pd particles vapor-deposited on an ultra-thin crystalline silica film grown on Mo(112) have been studied by scanning tunneling microscopy, X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, and temperature-programmed desorption of CO. No preferential nucleation of Pd on the silica film is found at room temperature deposition: the hemispherical Pd nanoparticles are homogenously dispersed on the support at all coverages studied (0.01-1ML(mono layer)). The Pd particles are resistant toward sintering up to 700K as judged by STM; however, CO adsorption studies have revealed surface chemical modification at temperatures as low as 550K. Strong morphological changes are observed above 800K (ultimately resulting in elongated rectangular islands at similar to 1000 K), which is accompanied by strong alterations of CO adsorption properties. The results are rationalized in terms of Pd and Mo substrate interdiffusion at elevated temperatures, while the silica film basically preserves its structure.
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| 8. |
- Sierka, M., et al.
(författare)
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Interplay between theory and experiment in the quest for silica with reduced dimensionality grown on a Mo(112) surface
- 2006
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 424:1-3, s. 115-119
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Tidskriftsartikel (refereegranskat)abstract
- The stability of ordered one- and two-dimensional silica structures formed on a Mo(112) surface as a function of silicon coverage and oxygen pressure (phase diagram) is derived from density functional theory. At elevated oxygen pressures formation of a new, previously not considered structure of two-dimensional silica film is predicted. It contains additional oxygen atoms adsorbed directly on the Mo(112) surface underneath a two-dimensional network of corner sharing [SiO4] tetrahedra. The existence of the new phase is confirmed experimentally using infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy.
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| 9. |
- Stacchiola, D. J., et al.
(författare)
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Growth of stoichiometric subnanometer silica films
- 2008
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Ingår i: Applied Physics Letters. - : AIP Publishing. - 0003-6951 .- 1077-3118. ; 92:1
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Tidskriftsartikel (refereegranskat)abstract
- We present a method to grow stoichiometric SiO(2) films of only similar to 0.6-0.9 nm in thickness on a metal substrate. Based on photoelectron and infrared spectroscopy studies, we conclude that the similar to 0.6-nm-thick silica films exhibit characteristics only observed for > 2.0-nm-thick films grown on conventional Si substrates. The films can be used as model oxides for fundamental studies and may have implications on the further miniaturization of metal-oxide-semiconductor transistors.
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| 10. |
- Gustafson, Johan, et al.
(författare)
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One-dimensional PtO(2) at Pt steps : Formation and reaction with CO
- 2005
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 95:25, s. 1-4
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Tidskriftsartikel (refereegranskat)abstract
- Using core-level spectroscopy and density functional theory we show that a one-dimensional (1D) PtO(2) oxide structure forms at the steps of the Pt(332) surface after O(2) exposure. The 1D oxide is found to be stable in an oxygen pressure range, where bulk oxides are only metastable, and is therefore argued to be a precursor to the Pt oxidation. As an example of the consequences of such a precursor exclusively present at the steps, we investigate the reaction of CO with oxygen covered Pt(332). Albeit more strongly bound, the oxidic oxygen is found to react more easily with CO than oxygen chemisorbed on the Pt terraces.
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| 11. |
- Kaya, S., et al.
(författare)
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Formation of one-dimensional molybdenum oxide on Mo(112)
- 2008
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 602:21, s. 3338-3342
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Tidskriftsartikel (refereegranskat)abstract
- The atomic structure of a reconstructed Mo(112)-O(2 x 3) surface has been revisited using photoelectron spectroscopy with synchrotron radiation, scanning tunneling microscopy, infrared reflection absorption spectroscopy and density functional theory. In contrast to previous models, the results are rationalized in terms of the formation of one-dimensional, Mo=O terminated molybdenum oxide involving corner sharing distorted [MoO(6)] octahedra on the (1 x 3) reconstructed Mo(112) surface.
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| 12. |
- Kaya, S., et al.
(författare)
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On the geometrical and electronic structure of an ultra-thin crystalline silica film grown on Mo(112)
- 2007
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 601:21, s. 4849-4861
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Tidskriftsartikel (refereegranskat)abstract
- The atomic structure of a well-ordered silica film grown on a Mo(112) single crystal substrate is discussed in detail using the experimental and theoretical results available to date. New photoelectron spectroscopy results using synchrotron radiation and ultraviolet spectroscopy data are presented. The analysis unambiguously shows that the ultra-thin silica film consists of a two-dimensional network of corner-sharing [SiO4] tetrahedra chemisorbed on the unreconstructed Mo(112) surface. The review also highlights the important role of theoretical calculations in the determination of the atomic structure of the silica films and in interpretation of experimental data.
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| 13. |
- Baber, Ashleigh E., et al.
(författare)
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In Situ Imaging of Cu2O under Reducing Conditions : Formation of Metallic Fronts by Mass Transfer
- 2013
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 135:45, s. 16781-16784
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Tidskriftsartikel (refereegranskat)abstract
- Active catalytic sites have traditionally been analyzed based on static representations of surface structures and characterization of materials before or after reactions. We show here by a combination of in situ microscopy and spectroscopy techniques that, in the presence of reactants, an oxide catalyst's chemical state and morphology are dynamically modified. The reduction of Cu2O films is studied under ambient pressures (AP) of CO. The use of complementary techniques allows us to identify intermediate surface oxide phases and determine how reaction fronts propagate across the surface by massive mass transfer of Cu atoms released during the reduction of the oxide phase in the presence of CO. High resolution in situ imaging by AP scanning tunneling microscopy (AP-STM) shows that the reduction of the oxide films is initiated at defects both on step edges and the center of oxide terraces.
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| 14. |
- Baber, Ashleigh E., et al.
(författare)
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Stabilization of Catalytically Active Cu plus Surface Sites on TitaniumCopper Mixed-Oxide Films**
- 2014
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Ingår i: Angewandte Chemie International Edition. - : Gesellschaft Deutscher Chemiker. - 1433-7851 .- 1521-3773. ; 53:21, s. 5336-5340
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Tidskriftsartikel (refereegranskat)abstract
- The oxidation of CO is the archetypal heterogeneous catalytic reaction and plays a central role in the advancement of fundamental studies, the control of automobile emissions, and industrial oxidation reactions. Copper-based catalysts were the first catalysts that were reported to enable the oxidation of CO at room temperature, but a lack of stability at the elevated reaction temperatures that are used in automobile catalytic converters, in particular the loss of the most reactive Cu+ cations, leads to their deactivation. Using a combined experimental and theoretical approach, it is shown how the incorporation of titanium cations in a Cu2O film leads to the formation of a stable mixed-metal oxide with a Cu+ terminated surface that is highly active for CO oxidation.
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| 15. |
- Evertsson, Jonas, et al.
(författare)
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The thickness of native oxides on aluminum alloys and single crystals
- 2015
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Ingår i: Applied Surface Science. - : Elsevier BV. - 1873-5584 .- 0169-4332. ; 349, s. 826-832
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Tidskriftsartikel (refereegranskat)abstract
- We present results from measurements of the native oxide film thickness on four different industrial aluminum alloys and three different aluminum single crystals. The thicknesses were determined using X-ray reflectivity, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. In addition, atomic force microscopy was used for micro-structural studies of the oxide surfaces. The reflectivity measurements were performed in ultra-high vacuum, vacuum, ambient, nitrogen and liquid water conditions. The results obtained using X-ray reflectivity and X-ray photoelectron spectroscopy demonstrate good agreement. However, the oxide thicknesses determined from the electrochemical impedance spectroscopy show a larger discrepancy from the above two methods. In the present contribution the reasons for this discrepancy are discussed. We also address the effect of the substrate type and the presence of water on the resultant oxide thickness.
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| 16. |
- Fashandi, Hossein, et al.
(författare)
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Monolayer iron oxide grown on porous platinum sensing layers of carbon monoxide sensors
- 2015
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Mono-layer iron oxide has been deposited through e-beam evaporation on a silica supported poly-crystalline platinum (Pt) model catalyst and its CO oxidation characteristics obtained from mass spectrometry measurements under various CO and O2 concentrations (ranging from 100 to 900 ppm and 3 to 7 %, respectively) as well as at different temperatures (ranging from 130 to 220 °C) and compared to the CO oxidation on corresponding non-coated Pt samples. Fabricating the model system as a Metal Oxide Semiconductor (MOS) structure from 4H-SiC with a top layer of SiO2 (as the support material) and a thin, discontinuous polycrystalline Pt film as the metal (the active catalyst material) also provided the possibility to investigate whether changes in catalyst surface conditions could be electronically monitored through the changes in capacitance they induce across the MOS structure.A low-temperature shift in the activity to CO oxidation for the iron oxide modified compared to bare Pt catalysts similar to what has previously been reported on single-crystalline Pt was found also for the near-realistic MOS model catalyst. This low-temperature shift was furthermore reflected in the electrical measurements, strongly indicating a correlation between the MOS capacitance and the CO oxidation characteristics, both in the case of iron oxide coated and non-coated Pt samples. By monitoring the MOS capacitance during more than 200 hours of continuous operation and analyzing the iron oxide coated samples by photo electron spectroscopy it could also be concluded that the iron oxide coated model catalyst seemingly retains its CO oxidation characteristics and chemical/compositional integrity over time. These findings might not only point to the applicability of iron oxide modified Pt in practical applications but may also open up new possibilities regarding the utilization of MOS model systems in studying and understanding as well as tailor CO oxidation (and other) catalysts and/or gas sensors for specific applications.
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| 17. |
- Halldin Stenlid, Joakim, et al.
(författare)
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Reactivity at the Cu2O(100):Cu-H2O interface : a combined DFT and PES study
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 18:44, s. 30570-30584
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Tidskriftsartikel (refereegranskat)abstract
- The water-cuprite interface plays an important role in dictating surface related properties. This not only applies to the oxide, but also to metallic copper, which is covered by an oxide film under typical operational conditions. In order to extend the currently scarce knowledge of the details of the water-oxide interplay, water interactions and reactions on a common Cu2O(100):Cu surface have been studied using high-resolution photoelectron spectroscopy (PES) as well as Hubbard U and dispersion corrected density functional theory (PBE-D3+U) calculations up to a bilayer water coverage. The PBE-D3+U results are compared with PBE, PBE-D3 and hybrid HSE06-D3 calculation results. Both computational and experimental results support a thermodynamically favored, and H2O coverage independent, surface OH coverage of 0.25-0.5 ML, which is larger than the previously reported value. The computations indicate that the results are consistent also for ambient temperatures under wet/humid and oxygen lean conditions. In addition, both DFT and PES results indicate that the initial (3,0; 1,1) surface reconstruction is lifted upon water adsorption to form an unreconstructed (1 x 1) Cu2O(100) structure.
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| 18. |
- Ji, Shaozheng, et al.
(författare)
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Influence of cathode geometry on electron dynamics in an ultrafast electron microscope
- 2017
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Ingår i: Structural Dynamics. - : American Crystallographic Association. - 2329-7778. ; 4:5
-
Tidskriftsartikel (refereegranskat)abstract
- Efforts to understand matter at ever-increasing spatial and temporal resolutions have led to the development of instruments such as the ultrafast transmission electron microscope (UEM) that can capture transient processes with combined nanometer and picosecond resolutions. However, analysis by UEM is often associated with extended acquisition times, mainly due to the limitations of the electron gun. Improvements are hampered by tradeoffs in realizing combinations of the conflicting objectives for source size, emittance, and energy and temporal dispersion. Fundamentally, the performance of the gun is a function of the cathode material, the gun and cathode geometry, and the local fields. Especially shank emission from a truncated tip cathode results in severe broadening effects and therefore such electrons must be filtered by applying a Wehnelt bias. Here we study the influence of the cathode geometry and the Wehnelt bias on the performance of a photoelectron gun in a thermionic configuration. We combine experimental analysis with finite element simulations tracing the paths of individual photoelectrons in the relevant 3D geometry. Specifically, we compare the performance of guard ring cathodes with no shank emission to conventional truncated tip geometries. We find that a guard ring cathode allows operation at minimum Wehnelt bias and improve the temporal resolution under realistic operation conditions in an UEM. At low bias, the Wehnelt exhibits stronger focus for guard ring than truncated tip cathodes. The increase in temporal spread with bias is mainly a result from a decrease in the accelerating field near the cathode surface. Furthermore, simulations reveal that the temporal dispersion is also influenced by the intrinsic angular distribution in the photoemission process and the initial energy spread. However, a smaller emission spot on the cathode is not a dominant driver for enhancing time resolution. Space charge induced temporal broadening shows a close to linear relation with the number of electrons up to at least 10 000 electrons per pulse. The Wehnelt bias will affect the energy distribution by changing the Rayleigh length, and thus the interaction time, at the crossover.
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| 19. |
- Kaya, S., et al.
(författare)
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Formation of an ordered ice layer on a thin silica film
- 2007
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 111:2, s. 759-764
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Tidskriftsartikel (refereegranskat)abstract
- Adsorption of water on a thin silica film grown on a Mo(112) single crystal was studied by temperature-programmed desorption, infrared reflection absorption spectroscopy, and photoelectron spectroscopy using synchrotron radiation. Water does not dissociate on the defect-free oxygen-terminated silica surface. In contrast to adsorption at 100 K, where water follows a zero-order desorption kinetics, water adsorbed at 140 K exhibits a pseudo-first-order kinetics and induces a strong blue shift of the silica phonon. Even larger spectral changes were observed for D2O adsorption. The results were rationalized in terms of the formation of an amorphous solid water film at 100 K and a crystalline ice monolayer film at 140-150 K. This film is well-ordered as revealed by low-energy electron diffraction showing a c(2 x 2) superstructure with respect to the silica substrate.
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| 20. |
- Kaya, S., et al.
(författare)
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Ice-assisted preparation of silica-supported vanadium oxide particles
- 2007
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 111:14, s. 5337-5344
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Tidskriftsartikel (refereegranskat)abstract
- Vanadium oxide particles were prepared by physical vapor deposition of vanadium in oxygen ambient onto ice-precovered well-ordered silica thin films. Morphology, electronic structure, and vibrational properties of the vanadia deposits were studied by scanning tunneling microscopy, X-ray photoelectron spectroscopy, temperature-programmed desorption, and infrared reflection absorption spectroscopy. The results show that the ice behaves as an oxidative agent, that favors vanadium oxidation up to V4+, and as a buffer layer that precludes strong interaction of the V adatoms with the silica film. At room temperature, upon desorption of the unreacted water, nanosized particles of vanadia hydroxide-like gel, containing V-OH and, to a lesser extent, vanadyl (VO) species, are formed. Vacuum annealing at 550 K leads to the total dehydration and partial reduction of the particles to V2O3, which expose the V-terminated surface. Subsequent reoxidation in 10(-6) mbar of O-2 irreversibly transforms the surface to the VO terminated, that is, the same as for the reactive deposition onto the clean silica surface. The results suggest that the structure of silica-supported vanadia catalysts is determined by a calcination step and should be considered under low oxygen pressure conditions as vanadium sesquioxide nanoparticles with the VO terminated surface.
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| 21. |
- Lundgren, Edvin, et al.
(författare)
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The surface oxide as a source of oxygen on Rh(111)
- 2005
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 144:SI, s. 367-372
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Tidskriftsartikel (refereegranskat)abstract
- The reduction of a thin surface oxide on the Rh(1 1 1) surface by CO is studied in situ by photoemission spectroscopy, scanning tunneling microscopy, and density functional theory. CO molecules are found not to adsorb on the surface oxide at a sample temperature of 100 K, in contrast to on the clean and chemisorbed oxygen covered surface. Despite this behavior, the surface oxide may still be reduced by CO, albeit in a significantly different fashion as compared to the reduction of a phase containing only chemisorbed on surface oxygen. The experimental observations combined with theoretical considerations concerning the stability of the surface oxide, result in a model of the reduction process at these pressures suggesting that the surface oxide behaves as a source of oxygen for the CO-oxidation reaction.
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| 22. |
- Martynova, Y., et al.
(författare)
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CO Oxidation Over Monolayer Manganese Oxide Films on Pt(111)
- 2013
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Ingår i: Catalysis Letters. - : Springer. - 1011-372X .- 1572-879X. ; 143:11, s. 1108-1115
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Tidskriftsartikel (refereegranskat)abstract
- Ultrathin manganese oxide films grown on Pt(111) were examined in the low temperature CO oxidation reaction at near atmospheric pressures. Structural characterization was performed by X-ray photoelectron spectroscopy, Auger electron spectroscopy, high-resolution electron energy loss spectroscopy, and temperature programmed desorption. The results show that the reactivity of MnOx ultrathin films is governed by a weakly bonded oxygen species, which may even be formed at low oxygen pressures (similar to 10(-6) mbar). For stable catalytic performance at realistic conditions the films required highly oxidizing conditions (CO:O-2 < 1:10), otherwise the films dewetted, ultimately resulting in the catalyst deactivation. Comparison with other thin films on Pt(111) shows, that the desorption temperature of weakly bonded oxygen species can be used as a benchmark for its activity in this reaction.
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| 23. |
- Mikkelsen, Anders, et al.
(författare)
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The influence of lysine on InP(001) surface ordering and nanowire growth
- 2005
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Ingår i: Nanotechnology. - : IOP Publishing. - 0957-4484 .- 1361-6528. ; 16:10, s. 2354-2359
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Tidskriftsartikel (refereegranskat)abstract
- We report on high resolution photoelectron core level spectroscopy (HRCLS) and scanning tunnelling microscopy (STM) measurements of the decomposition of lysine adsorbed on InP(001) substrates. We find that components from the lysine can be present on the InP surface even after annealing to 600 degrees C and desorption of the native surface oxide. We further observe that while a crystalline surface phase can be observed on the epi-ready surface after annealing, the lysine treated surface still appears rough. We conclude that lysine residues inhibit the formation of a flat crystalline structure on the InP(001) surface. These results are discussed in terms of the lysine promotion of [001] nanowire growth.
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| 24. |
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| 25. |
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| 26. |
- Tissot, H., et al.
(författare)
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Acetic acid conversion to ketene on Cu 2 O(1 0 0): Reaction mechanism deduced from experimental observations and theoretical computations
- 2021
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Ingår i: Journal of Catalysis. - : Elsevier BV. - 0021-9517 .- 1090-2694. ; 402, s. 154-165
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Tidskriftsartikel (refereegranskat)abstract
- Ketene, a versatile reagent in production of fine and specialty chemicals, is produced from acetic acid. We investigate the synthesis of ketene from acetic acid over the (3,0;1,1) surface of Cu2O(1 0 0) through analysis of the adsorption and desorption characteristics of formic and acetic acids. The results allow us to establish a reaction mechanism for ketene formation. Observations from x-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy, and temperature programmed desorption (TPD), supported by a comparison with formic acid results, suggest that acetic acid reacts with Cu2O through deprotonation to form acetate species coordinated to copper sites and hydroxylation of nearby surface oxygen sites. For formic acid the decomposition of adsorbed formate species results in desorption of CO2 and CO while, for acetic acid, high yields of ketene are observed at temperature >500 K. Modeling by density functional theory (DFT) confirms the strong interaction of acetic acid with the (3,0;1,1) surface and the spontaneous dissociation into adsorbed acetate and hydrogen atom species, the latter forming an OH-group. In an identified reaction intermediate ketene binds via all C and O atoms to Cu surface sites, in agreement with interpretations from XPS. In the vicinity of the adsorbate the surface experiences a local reorganization into a c(2 × 2) reconstruction. The total computed energy barrier for ketene formation is 1.81 eV in good agreement with the 1.74 eV obtained from TPD analysis. Our experimental observations and mechanistic DFT studies suggests that Cu2O can operate as an efficient catalyst for the green generation of ketene from acetic acid.
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| 27. |
- Wang, Chunlei, et al.
(författare)
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Inverse single-site Fe1(OH)X/Pt(111) model catalyst for preferential oxidation of CO in H2
- 2022
-
Ingår i: Nano Reseach. - : Springer Nature. - 1998-0124 .- 1998-0000. ; 15:1, s. 709-715
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Tidskriftsartikel (refereegranskat)abstract
- Inverse oxide/metal model systems are frequently used to investigate catalytic structure-function relationships at an atomic level. By means of a novel atomic layer deposition process, growth of single-site Fe1Ox on a Pt(111) single crystal surface was achieved, as confirmed by scanning tunneling microscopy (STM). The redox properties of the catalyst were characterized by synchrotron radiation based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). After calcination treatment at 373 K in 1 mbar O2 the chemical state of the catalyst was determined as Fe3+. Reduction in 1 mbar H2 at 373 K demonstrates a facile reduction to Fe2+ and complete hydroxylation at significantly lower temperatures than what has been reported for iron oxide nanoparticles. At reaction conditions relevant for preferential oxidation of CO in H2 (PROX), the catalyst exhibits a Fe3+ state (ferric hydroxide) at 298 K while re-oxidation of iron oxide clusters does not occur under the same condition. CO oxidation proceeds on the single-site Fe1(OH)3 through a mechanism including the loss of hydroxyl groups in the temperature range of 373 to 473 K, but no reaction is observed on iron oxide clusters. The results highlight the high flexibility of the single iron atom catalyst in switching oxidation states, not observed for iron oxide nanoparticles under similar reaction conditions, which may indicate a higher intrinsic activity of such single interfacial sites than the conventional metal-oxide interfaces. In summary, our findings of the redox properties on inverse single-site iron oxide model catalyst may provide new insights into applied Fe-Pt catalysis. [Figure not available: see fulltext.]
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| 28. |
- Wang, Chunlei, et al.
(författare)
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Stabilization of Cu2O through Site-Selective Formation of a Co1Cu Hybrid Single-Atom Catalyst
- 2022
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 34:5, s. 2313-2320
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Tidskriftsartikel (refereegranskat)abstract
- Single-atom catalysts (SACs) consist of a low coverage of isolated metal atoms dispersed on a metal substrate, called single-atom alloys (SAAs), or alternatively single metal atoms coordinated to oxygen atoms on an oxide support. We present the synthesis of a new type of Co1Cu SAC centers on a Cu2O(111) support by means of a site-selective atomic layer deposition technique. Isolated metallic Co atoms selectively coordinate to the native oxygen vacancy sites (Cu sites) of the reconstructed Cu2O(111) surface, forming a Co1Cu SAA with no direct Co- Ox bonds. The centers, here referred to as Co1Cu hybrid SACs, are found to stabilize the active Cu+ sites of the low-cost Cu2O catalyst that otherwise is prone to deactivation under reaction conditions. The stability of the Cu2O(111) surface was investigated by synchrotron radiation-based ambient-pressure X-ray photoelectron spectroscopy under reducing CO environment. The structure and reduction reaction are modeled by density functional theory calculations, in good agreement with experimental results.
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| 29. |
- Xu, Fang, et al.
(författare)
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Redox-Mediated Reconstruction of Copper during Carbon Monoxide Oxidation
- 2014
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 118:29, s. 15902-15909
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Tidskriftsartikel (refereegranskat)abstract
- Copper has excellent initial activity for the oxidation of CO, yet it rapidly deactivates under reaction conditions. In an effort to obtain a full picture of the dynamic morphological and chemical changes occurring on the surface of catalysts under CO oxidation conditions, a complementary set of in situ ambient pressure (AP) techniques that include scanning tunneling microscopy, infrared reflection absorption spectroscopy (IRRAS), and X-ray photoelectron spectroscopy were conducted. Herein, we report in situ AP CO oxidation experiments over Cu(111) model catalysts at room temperature. Depending on the CO:O-2 ratio, Cu presents different oxidation states, leading to the coexistence of several phases. During CO oxidation, a redox cycle is observed on the substrate's surface, in which Cu atoms are oxidized and pulled from terraces and step edges and then are reduced and rejoin nearby step edges. IRRAS results confirm the presence of under-coordinated Cu atoms during the reaction. By using control experiments to isolate individual phases, it is shown that the rate for CO oxidation decreases systematically as metallic copper is fully oxidized.
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