| 1. |
- 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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| 2. |
- 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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| 3. |
- Duchon, Tomas, et al.
(författare)
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Establishing structure-sensitivity of ceria reducibility : real-time observations of surface hydrogen interactions
- 2020
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Ingår i: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 8:11, s. 5501-5507
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Tidskriftsartikel (refereegranskat)abstract
- The first Layer of atoms on an oxide cataLyst provides the first sites for adsorption of reactants and the Last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria cataLyst with different surface terminations under an H2 environment to unequivocally establish the effect of the Last Layer of atoms on surface reduction. (111) and (100) terminated epitaxiaL isLands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure reducibility relationship under identical conditions. Kinetic rate constants of Ce4+ to Ce3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of isLands, more pronounced oxygen release, and overall higher reducibility were observed for (100) isLands compared to (111) ones. The findings are in agreement with coordination -Limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts.
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| 4. |
- Grinter, David, et al.
(författare)
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Potassium promotion of a model Au/TiO2 catalyst
- 2016
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Ingår i: Abstracts of Papers of the American Chemical Society. - : AMER CHEMICAL SOC. - 0065-7727. ; 252
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)
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| 5. |
- Kettner, Miroslav, et al.
(författare)
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Anion-mediated electronic effects in reducible oxides : Tuning the valence band of ceria via fluorine doping
- 2019
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 151:4
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Tidskriftsartikel (refereegranskat)abstract
- Combining experimental spectroscopy and hybrid density functional theory calculations, we show that the incorporation of fluoride ions into a prototypical reducible oxide surface, namely, ceria(111), can induce a variety of nontrivial changes to the local electronic structure, beyond the expected increase in the number of Ce3+ ions. Our resonant photoemission spectroscopy results reveal new states above, within, and below the valence band, which are unique to the presence of fluoride ions at the surface. With the help of hybrid density functional calculations, we show that the different states arise from fluoride ions in different atomic layers in the near surface region. In particular, we identify a structure in which a fluoride ion substitutes for an oxygen ion at the surface, with a second fluoride ion on top of a surface Ce4+ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F--Ce4+ resonant enhancement feature suggests that this bond is at least partially covalent. Our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.
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| 6. |
- Kottwitz, Matthew, et al.
(författare)
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Local Structure and Electronic State of Atomically Dispersed Pt Supported on Nanosized CeO2
- 2019
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Ingår i: ACS Catalysis. - : AMER CHEMICAL SOC. - 2155-5435. ; 9:9, s. 8738-8748
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Tidskriftsartikel (refereegranskat)abstract
- Single atom catalysts (SACs) have shown high activity and selectivity in a growing number of chemical reactions. Many efforts aimed at unveiling the structure-property relationships underpinning these activities and developing synthesis methods for obtaining SACs with the desired structures are hindered by the paucity of experimental methods capable of probing the attributes of local structure, electronic properties, and interaction with support-features that comprise key descriptors of their activity. In this work, we describe a combination of experimental and theoretical approaches that include photon and electron spectroscopy, scattering, and imaging methods, linked by density functional theory calculations, for providing detailed and comprehensive information on the atomic structure and electronic properties of SACs. This characterization toolbox is demonstrated here using a model single atom Pt/CeO2 catalyst prepared via a sol-gel-based synthesis method. Isolated Pt atoms together with extra oxygen atoms passivate the (100) surface of nanosized ceria. A detailed picture of the local structure of Pt nearest environment emerges from this work involving the bonding of isolated Pt2+ ions at the hollow sites of perturbed (100) surface planes of the CeO2 support, as well as a substantial (and heretofore unrecognized) strain within the CeO2 lattice in the immediate vicinity of the Pt centers. The detailed information on structural attributes provided by our approach is the key for understanding and improving the properties of SACs.
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| 7. |
- Li, Yuanyuan, et al.
(författare)
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Active sites of atomically dispersed Pt supported on Gd-doped ceria with improved low temperature performance for CO oxidation
- 2023
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Ingår i: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 14:44, s. 12582-12588
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Tidskriftsartikel (refereegranskat)abstract
- “Single-atom” catalysts (SACs) have been the focus of intense research, due to debates about their reactivity and challenges toward determining and designing “single-atom” (SA) sites. To address the challenge, in this work, we designed Pt SACs supported on Gd-doped ceria (Pt/CGO), which showed improved activity for CO oxidation compared to its counterpart, Pt/ceria. The enhanced activity of Pt/CGO was associated with a new Pt SA site which appeared only in the Pt/CGO catalyst under CO pretreatment at elevated temperatures. Combined X-ray and optical spectroscopies revealed that, at this site, Pt was found to be d-electron rich and bridged with Gd-induced defects via an oxygen vacancy. As explained by density functional theory calculations, this site opened a new path via a dicarbonyl intermediate for CO oxidation with a greatly reduced energy barrier. These results provide guidance for rationally improving the catalytic properties of SA sites for oxidation reactions.
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| 8. |
- Li, Yuanyuan, et al.
(författare)
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Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction
- 2021
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Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 12:1
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Tidskriftsartikel (refereegranskat)abstract
- Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding-perhaps most importantly the temporal dynamic changes occurring therein-serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO2 system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt-0-O vacancy-Ce3+ sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction. Revealing the structure and dynamics of active sites is essential to understand catalytic mechanisms. Here the authors demonstrate the dynamic nature of perimeter Pt-0-O vacancy-Ce3+ sites in Pt/CeO2 and the key effects of their dynamics on the mechanism of the water gas shift reaction.
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| 9. |
- Wang, Haodong, et al.
(författare)
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Aliovalent Doping of CeO2 Improves the Stability of Atomically Dispersed Pt
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:44, s. 52736-52742
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Tidskriftsartikel (refereegranskat)abstract
- Atomically dispersed supported catalysts hold considerable promise as catalytic materials. The ability to employ and stabilize them against aggregation in complex process environments remains a key challenge to the elusive goal of 100% atom utilization in catalysis. Herein, using a Gd-doped ceria support for atomically dispersed surface Pt atoms, we establish how the combined effects of aliovalent doping and oxygen vacancy generation provide dynamic mechanisms that serve to enhance the stability of supported single-atom configurations. Using correlated, in situ X-ray absorption, photoelectron, and vibrational spectroscopy methods for the analysis of samples on the two types of support (with and without Gd doping), we establish that the Pt atoms are located proximal to Gd dopants, forming a speciation that serves to enhance the thermal stability of Pt atoms against aggregation.
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