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1.
Faraday Discuss ; 245(0): 164-180, 2023 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-37334658

RESUMO

We report Atacama Large Millimeter/submillimeter Array (ALMA) high-angular resolution (∼50 au) observations of the binary system SVS13-A. More specifically, we analyse deuterated water (HDO) and sulfur dioxide (SO2) emission. The molecular emission is associated with both the components of the binary system, VLA4A and VLA4B. The spatial distribution is compared to that of formamide (NH2CHO), previously analysed in the system. Deuterated water shows an additional emitting component spatially coincident with the dust-accretion streamer, at a distance ≥120 au from the protostars, and at blue-shifted velocities (>3 km s-1 from the systemic velocities). We investigate the origin of the molecular emission in the streamer, in light of thermal sublimation temperatures calculated using updated binding energy (BE) distributions. We propose that the observed emission is produced by an accretion shock at the interface between the accretion streamer and the disk of VLA4A. Thermal desorption is not completely excluded in case the source is actively experiencing an accretion burst.

2.
J Phys Chem B ; 126(26): 4948-4955, 2022 07 07.
Artigo em Inglês | MEDLINE | ID: mdl-35748647

RESUMO

Hydrophobic cluster structures in aqueous ethanol solutions at different concentrations have been investigated by soft X-ray absorption spectroscopy (XAS). In the O K-edge XAS, we have found that hydrogen bond structures among water molecules are enhanced in the middle-concentration region by the hydrophobic interaction of the ethyl groups in ethanol. In the C K-edge XAS, the lower energy features arise from a transition from the terminal methyl C 1s electron to an unoccupied orbital of 3s Rydberg character, which is sensitive to the nearest-neighbor intermolecular interactions. From the comparison of C K-edge XAS with the inner-shell calculations, we have found that ethanol clusters are easily formed in the middle-concentration region due to the hydrophobic interaction of the ethyl group in ethanol, resulting in the enhancement of the hydrogen bond structures among water molecules. This behavior is different from aqueous methanol solutions, where the methanol-water mixed clusters are more predominant in the middle-concentration region due to the relatively weak hydrophobic interactions of the methyl group in methanol.


Assuntos
Etanol , Metanol , Interações Hidrofóbicas e Hidrofílicas , Água/química , Espectroscopia por Absorção de Raios X
3.
ACS Catal ; 12(6): 3256-3268, 2022 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-35359579

RESUMO

Co oxides and oxyhydroxides have been studied extensively in the past as promising electrocatalysts for the oxygen evolution reaction (OER) in neutral to alkaline media. Earlier studies showed the formation of an ultrathin CoO x (OH) y skin layer on Co3O4 at potentials above 1.15 V vs reversible hydrogen electrode (RHE), but the precise influence of this skin layer on the OER reactivity is still under debate. We present here a systematic study of epitaxial spinel-type Co3O4 films with defined (111) orientation, prepared on different substrates by electrodeposition or physical vapor deposition. The OER overpotential of these samples may vary up to 120 mV, corresponding to two orders of magnitude differences in current density, which cannot be accounted for by differences in the electrochemically active surface area. We demonstrate by a careful analysis of operando surface X-ray diffraction measurements that these differences are clearly correlated with the average thickness of the skin layer. The OER reactivity increases with the amount of formed skin layer, indicating that the entire three-dimensional skin layer is an OER-active interphase. Furthermore, a scaling relationship between the reaction centers in the skin layer and the OER activity is established. It suggests that two lattice sites are involved in the OER mechanism.

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