| 1. |
- Armillotta, Francesco, et al.
(författare)
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Single Metal Atom Catalysts and ORR : H-Bonding, Solvation, and the Elusive Hydroperoxyl Intermediate
- 2022
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 12:13, s. 7950-7959
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Tidskriftsartikel (refereegranskat)abstract
- The widely investigated oxygen reduction reaction (ORR) is well-known to proceed via two competing routes, involving two or four electrons, and yielding different reaction products, respectively. Both pathways are believed to share a common, elusive intermediate, namely, the hydroperoxyl radical. By exploiting a cobalt single-atom biomimetic model catalyst, based on a self-assembled monolayer of Co-porphyrins grown on an almost free-standing graphene sheet, we identify, in situ at room temperature in O2+H2O atmosphere, a hydroperoxyl-water cluster that is stabilized at the Co single-metal atom catalytic site. We show that the interplay between charge transfer, dipole and H-bonding, and water solvation behavior actually determines the hydroperoxyl-water complex stability, the Co-OOH bonding geometry, and, prospectively, opens to the engineered control of the selectivity of ORR pathways.
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| 2. |
- Baraldi, Alessandro, et al.
(författare)
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The (1x1)-> hexagonal structural transition on Pt(100) studied by high-energy resolution core level photoemission
- 2007
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 127:16
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Tidskriftsartikel (refereegranskat)abstract
- The (1 x 1)-> quasihexagonal (HEX) phase transition on a clean Pt(100) surface was investigated by monitoring the time evolution of the Pt4f(7/2) core level photoemission spectra. The spectral component originating from the atoms forming the (1 x .1) metastable unreconstructed surface was found at -570 +/- 20 meV with respect to the bulk peak. Ab initio calculations based on density functional theory confirmed the experimental assignment. At temperatures above 370 K, the (1 x 1) phase irreversibly reverts to the more stable HEX phase, characterized by a surface core level shifted component at -185 +/- 40 meV. By analyzing the intensity evolution of the core level components, measured at different temperatures in the range of 393-475 K, we determined the activation energy of the phase transformation, E=0.76 +/- 0.04 eV. This value is considerably lower than the one previously determined by means of low energy electron diffraction. Possible reasons for this discrepancy are discussed.
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| 3. |
- Biasin, Pietro, et al.
(författare)
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From borophene polymorphs towards a single honeycomb borophane phase : reduction of hexagonal boron layers on Al(111)
- 2023
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Ingår i: Nanoscale. - 2040-3364. ; 15:45, s. 18407-18414
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Tidskriftsartikel (refereegranskat)abstract
- The recent interest in characterizing 2D boron polymorphs has led to claims of the first stabilization of a honeycomb phase with conical Dirac-like electron dispersion. However, the synthesis of chemically stable, single, and homogeneous 2D boron phases still represents a significant experimental challenge. This is ascribed to the intrinsic boron electronic configuration that, at variance with carbon, leads to the formation of multi-center covalent bonds. External charge compensation by substrate-induced doping can steer the geometry of the layer, both in the buckling and in the density of B vacancies, like in the case of the recently achieved stabilization of honeycomb boron layers on Al(111). The price to pay is however a strong boron-support interaction, resulting in general in a limiting kinetic hindrance with respect to the synthesis of homogenous single phases. In the specific case of Al(111) an AlB2 layer is known to form at the surface, quite far from a desirable quasi-freestanding borophene monolayer and at variance with graphene, which can be easily synthesized in an almost freestanding configuration e.g. on Ir(111). We provide here evidence for the (reversible) formation of well-ordered honeycomb borophane upon hydrogenation of the honeycomb boron phase on Al(111).
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| 4. |
- Biasin, Pietro, et al.
(författare)
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Growth and Redox Properties of Boron on Al(111) : Competing Affinities in the Case of Honeycomb AlB2
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Ingår i: ACS Nano. - 1936-0851.
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Tidskriftsartikel (refereegranskat)abstract
- The complexity of the geometric and electronic structure of boron allotropes is associated with the multicentric bonding character and the consequent B polymorphism. When growth is limited to two-dimensions (2D), the structural and electronic confinement yields the borophenes family, where the interaction with the templating substrate actually determines the stability of inequivalent boron phases. We report here a detailed study of the growth of the honeycomb AlB2 phase on Al(111), followed by an investigation of its oxidation and reduction properties. By means of a combined experimental and theoretical approach, we show that the structure of the B/Al interface is affected by the complex interplay between B, Al, and common reactive agents like oxygen and hydrogen. While kinetic effects associated with diffusion and strain release influence the AlB2 growth in vacuo, Al, B, O, and H chemical affinities determine its redox behavior. Reduction with atomic hydrogen involves the B layer and yields an ordered honeycomb borophane H/AlB2 phase. Instead, oxidation takes place at the Al interface, giving origin to buried and 1D surface aluminum oxide phases.
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| 5. |
- Pramhaas, Verena, et al.
(författare)
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Interplay between CO Disproportionation and Oxidation: On the Origin of the CO Reaction Onset on Atomic Layer Deposition-Grown Pt/ZrO2Model Catalysts
- 2021
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 11:1, s. 208-214
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Tidskriftsartikel (refereegranskat)abstract
- Pt/ZrO2 model catalysts were prepared by atomic layer deposition (ALD) and examined at mbar pressure by operando sum frequency generation (SFG) spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) combined with differentially pumped mass spectrometry (MS). ALD enables creating model systems ranging from Pt nanoparticles to bulk-like thin films. Polarization-dependent SFG of CO adsorption reveals both the adsorption configuration and the Pt particle morphology. By combining experimental data with ab initio density functional theory (DFT) calculations, we show that the CO reaction onset is determined by a delicate balance between CO disproportionation (Boudouard reaction) and oxidation. CO disproportionation occurs on low-coordinated Pt sites, but only at high CO coverages and when the remaining C atom is stabilized by a favorable coordination. Thus, under the current conditions, initial CO oxidation is found to be strongly influenced by the removal of carbon deposits formed through disproportionation mechanisms rather than being determined by the CO and oxygen inherent activity. Accordingly, at variance with the general expectation, rough Pt nanoparticles are seemingly less active than smoother Pt films. The applied approach enables bridging both the "materials and pressure gaps".
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