| 1. |
- Goodwin, Christopher M., 1989-, et al.
(författare)
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Operando Probing of the Surface Chemistry During the Haber-Bosch Process
- 2024
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Ingår i: Nature. - 0028-0836 .- 1476-4687. ; 625:7994, s. 282-286
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Tidskriftsartikel (refereegranskat)abstract
- The Haber-Bosch process produces NH3 from N2 and H21,2, typically with Fe and Ru3. HB has been proposed as the most important scientific invention in the 20th century4. The chemical state during reaction has been proposed as oxides5, nitrides2, metallic, or surface nitride6. The proposed rate-limiting step has been the dissociation of N27–9, reaction of adsorbed nitrogen10, or desorption of NH311. Due to the vacuum requirement for surface-sensitive techniques, studies at reaction conditions are limited to theory computations12–14. We determined the surface composition, during NH3 production, at pressures up to 1 bar and temperatures as high as 723 K on flat, stepped Fe, and stepped Ru single crystal surfaces using operando X-ray Photoelectron Spectroscopy15. We found that all surfaces remain metallic. On Fe only a small amount of adsorbed N remains, yet Ru’s surface is almost adsorbate free. At 523 K, high amines (NHx) coverages appear on the stepped Fe surface. The results show that the rate-limiting step on Ru is always N2 dissociation. Still, on Fe the hydrogenation step involving adsorbed N atoms is essential for the total rate, as predicted by theory13. If the temperature is lowered on Fe, the rate-limiting steps switch and become surface species’ hydrogenation.
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| 2. |
- Boscolo Bibi, Sara, 1993-, et al.
(författare)
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Multi-spectroscopic study of electrochemically-formed oxide-derived gold electrodes
- 2024
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 26:3, s. 2332-2340
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Tidskriftsartikel (refereegranskat)abstract
- Oxide-derived metals are produced by reducing an oxide precursor. These materials, including gold, have shown improved catalytic performance over many native metals. The origin of this improvement for gold is not yet understood. In this study, operando non-resonant sum frequency generation (SFG) and ex situ high-pressure X-ray photoelectron spectroscopy (HP-XPS) have been employed to investigate electrochemically-formed oxide-derived gold (OD-Au) from polycrystalline gold surfaces. A range of different oxidizing conditions were used to form OD-Au in acidic aqueous medium (H3PO4, pH = 1). Our electrochemical data after OD-Au is generated suggest that the surface is metallic gold, however SFG signal variations indicate the presence of subsurface gold oxide remnants between the metallic gold surface layer and bulk gold. The HP-XPS results suggest that this subsurface gold oxide could be in the form of Au2O3 or Au(OH)3. Furthermore, the SFG measurements show that with reducing electrochemical treatments the original gold metallic state can be restored, meaning the subsurface gold oxide is released. This work demonstrates that remnants of gold oxide persist beneath the topmost gold layer when the OD-Au is created, potentially facilitating the understanding of the improved catalytic properties of OD-Au.
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| 3. |
- Degerman, David, 1989-, et al.
(författare)
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Effect of CO2-Rich Syngas on the Chemical State of Fe(110) during Fischer-Tropsch Synthesis
- 2024
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Ingår i: The Journal of Physical Chemistry C. - 1932-7447 .- 1932-7455. ; 128:13, s. 5542-5552
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Tidskriftsartikel (refereegranskat)abstract
- We have used in situ X-ray photoelectron spectroscopy to obtain information about the chemical state of a Fe single-crystal catalyst upon addition of CO2 in the syngas feed during Fischer–Tropsch synthesis (FTS) between 85 and 550 mbar. We found that at certain temperatures, the ternary mixture of CO, CO2, and H2 yields a chemical state which is resemblant of neither the CO hydrogenation nor the CO2 hydrogenation reaction mixtures in isolation. The addition of CO2 to a CO + H2 reaction mixture mostly affects the chemical state at low-temperature FTS conditions (i.e., below 254 °C). In this temperature span, the ternary reaction mixture resulted in a carburized surface, whereas the CO + H2 reaction led to surface oxidation. We propose a hypothesis, where a carbonate intermediate produced by CO2 interaction with Fe oxide aids the reduction of the Fe oxide, paving the way for the carburization of the Fe by dissociated CO. Very small differences in the spectra of the CO + H2 and the CO + CO2 + H2 reaction mixtures were observed above 254 °C, suggesting that the CO2 is a spectator in these conditions. Changing the total pressure of both the CO hydrogenation and ternary reaction mixture causes quantitative changes in the spectra at both low- and high-temperature FTS conditions, the degree of oxidation/carburization was affected in the low-temperature-FTS regime, and the degree of hydrocarbon build-up was affected in the high-temperature-FTS.
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| 4. |
- Degerman, David, 1989-, et al.
(författare)
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Operando Observation of Oxygenated Intermediates during CO Hydrogenation on Rh Single Crystals
- 2022
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 144:16, s. 7038-7042
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Tidskriftsartikel (refereegranskat)abstract
- The CO hydrogenation reaction over the Rh(111) and (211) surfaces has been investigated operando by X-ray photoelectron spectroscopy at a pressure of 150 mbar. Observations of the resting state of the catalyst give mechanistic insight into the selectivity of Rh for generating ethanol from CO hydrogenation. This study shows that the Rh(111) surface does not dissociate all CO molecules before hydrogenation of the O and C atoms, which allows methoxy and other both oxygenated and hydrogenated species to be visible in the photoelectron spectra.
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| 5. |
- Shipilin, Mikhail, et al.
(författare)
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In Situ Surface-Sensitive Investigation of Multiple Carbon Phases on Fe(110) in the Fischer-Tropsch Synthesis
- 2022
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 12:13, s. 7609-7621
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Tidskriftsartikel (refereegranskat)abstract
- Carbide formation on iron-based catalysts is an integral and, arguably, the most important part of the Fischer–Tropsch synthesis process, converting CO and H2 into synthetic fuels and numerous valuable chemicals. Here, we report an in situ surface-sensitive study of the effect of pressure, temperature, time, and gas feed composition on the growth dynamics of two distinct iron–carbon phases with the octahedral and trigonal prismatic coordination of carbon sites on an Fe(110) single crystal acting as a model catalyst. Using a combination of state-of-the-art X-ray photoelectron spectroscopy at an unprecedentedly high pressure, high-energy surface X-ray diffraction, mass spectrometry, and theoretical calculations, we reveal the details of iron surface carburization and product formation under semirealistic conditions. We provide a detailed insight into the state of the catalyst’s surface in relation to the reaction.
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| 6. |
- Amann, Peter, et al.
(författare)
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The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst
- 2022
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 376:6593, s. 603-608
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Tidskriftsartikel (refereegranskat)abstract
- The active chemical state of zinc (Zn) in a zinc-copper (Zn-Cu) catalyst during carbon dioxide/carbon monoxide (CO2/CO) hydrogenation has been debated to be Zn oxide (ZnO) nanoparticles, metallic Zn, or a Zn-Cu surface alloy. We used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO2/CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface. Tuning of the grazing incidence angle makes it possible to achieve either surface or bulk sensitivity. Hydrogenation of CO2 gives preference to ZnO in the form of clusters or nanoparticles, whereas in pure CO a surface Zn-Cu alloy becomes more prominent. The results reveal a specific role of CO in the formation of the Zn-Cu surface alloy as an active phase that facilitates efficient CO2 methanol synthesis.
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| 7. |
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| 8. |
- Gleißner, Robert, et al.
(författare)
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Role of Oxidation–Reduction Dynamics in the Application of Cu/ZnO-Based Catalysts
- 2023
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Ingår i: ACS Applied Nano Materials. - 2574-0970. ; 6:9, s. 8004-8016
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Tidskriftsartikel (refereegranskat)abstract
- We investigated Cu nanoparticles (NPs) on vicinal and basal ZnO supports to obtain an atomistic picture of the catalyst’s structure under in situ oxidizing and reducing conditions. The Cu/ZnO model catalysts were investigated at elevated gas pressures by high energy grazing incidence X-ray diffraction and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). We find that the Cu nanoparticles are fully oxidized to Cu2O under atmospheric conditions at room temperature. As the nanoparticles swell during oxidation, they maintain their epitaxy on basal ZnO (000 ± 1) surfaces, whereas on the vicinal ZnO (101̅4) surface, the nanoparticles undergo a coherent tilt. We find that the oxidation process is fully reversible under H2 flow at 500 K, resulting in predominantly well-aligned nanoparticles on the basal surfaces, whereas the orientation of Cu NPs on vicinal ZnO was only partially restored. The analysis of the substrate crystal truncation rods evidences the stability of basal ZnO surfaces under all gas conditions. No Cu–Zn bulk alloy formation is observed. Under CO2 flow, no diffraction signal from the nanoparticles is detected, pointing to their completely disordered state. The AP-XPS results are in line with the formation of CuO. Scanning electron microscopy images show that massive mass transport has set in, leading to the formation of larger agglomerates.
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