Investigation of atomically precise Au nanoclusters provides a route to understand the roles of coordination, size, and ligand effects on Au catalysis. Herein, we explored the catalytic behavior of a ...newly synthesized Au22(L8)6 nanocluster (L = 1,8-bis(diphenylphosphino) octane) with in situ uncoordinated Au sites supported on TiO2, CeO2, and Al2O3. Stability of the supported Au22 nanoclusters was probed structurally by in situ extended X-ray absorption fine structure (EXAFS) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and their ability to adsorb and oxidize CO was investigated by IR absorption spectroscopy and a temperature-programmed flow reaction. Low-temperature CO oxidation activity was observed for the supported pristine Au22(L8)6 nanoclusters without ligand removal. Density functional theory (DFT) calculations confirmed that the eight uncoordinated Au sites in the intact Au22(L8)6 nanoclusters can chemisorb both CO and O2. Use of isotopically labeled O2 demonstrated that the reaction pathway occurs mainly through a redox mechanism, consistent with the observed support-dependent activity trend of CeO2 > TiO2 > Al2O3. We conclude that the uncoordinated Au sites in the intact Au22(L8)6 nanoclusters are capable of adsorbing CO, activating O2, and catalyzing CO oxidation reaction. This work is the first clear demonstration of a ligand-protected intact Au nanocluster that is active for gas-phase catalysis without the need of ligand removal.
The ability to direct bimetallic nanoparticles to express desirable surface composition is a crucial step toward effective heterogeneous catalysis, sensing, and bionanotechnology applications. Here ...we report surface composition tuning of bimetallic Au–Pt electrocatalysts for carbon monoxide and methanol oxidation reactions. We establish a direct correlation between the surface composition of Au–Pt nanoparticles and their catalytic activities. We find that the intrinsic activities of Au–Pt nanoparticles with the same bulk composition of Au0.5Pt0.5 can be enhanced by orders of magnitude by simply controlling the surface composition. We attribute this enhancement to the weakened CO binding on Pt in discrete Pt or Pt-rich clusters surrounded by surface Au atoms. Our finding demonstrates the importance of surface composition control at the nanoscale in harnessing the true electrocatalytic potential of bimetallic nanoparticles and opens up strategies for the development of highly active bimetallic nanoparticles for electrochemical energy conversion.
Brown dwarfs--substellar bodies more massive than planets but not massive enough to initiate the sustained hydrogen fusion that powers self-luminous stars--are born hot and slowly cool as they age. ...As they cool below about 2,300 kelvin, liquid or crystalline particles composed of calcium aluminates, silicates and iron condense into atmospheric 'dust', which disappears at still cooler temperatures (around 1,300 kelvin). Models to explain this dust dispersal include both an abrupt sinking of the entire cloud deck into the deep, unobservable atmosphere and breakup of the cloud into scattered patches (as seen on Jupiter and Saturn). However, hitherto observations of brown dwarfs have been limited to globally integrated measurements, which can reveal surface inhomogeneities but cannot unambiguously resolve surface features. Here we report a two-dimensional map of a brown dwarf's surface that allows identification of large-scale bright and dark features, indicative of patchy clouds. Monitoring suggests that the characteristic timescale for the evolution of global weather patterns is approximately one day.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Context. Being the most numerous and oldest stars in the galaxy, M dwarfs are objects of great interest for exoplanet searches. The presence of molecules in their atmosphere complicates our ...understanding of their atmospheric properties. But great advances have recently been made in the modeling of M dwarfs due to the revision of solar abundances. Aims. We aim to determine stellar parameters of M dwarfs using high resolution spectra (R ∼ 90 000) simultaneously in the visible and the near-infrared. The high resolution spectra and broad wavelength coverage provide an unique opportunity to understand the onset of dust and cloud formation at cool temperatures. Furthermore, this study will help in understanding the physical processes which occur in a cool atmospheres, particularly, the redistribution of energy from the optical to the near-infrared. Methods. The stellar parameters of M dwarfs in our sample have been determined by comparing the high resolution spectra both in the optical and in the near-infrared simultaneously observed by CARMENES with the synthetic spectra obtained from the BT-Settl model atmosphere. The detailed spectral synthesis of these observed spectra both in the optical and in the near-infrared helps to understand the missing continuum opacity. Results. For the first time, we derive fundamental stellar parameters of M dwarfs using the high resolution optical and near-infrared spectra simultaneously. We determine Teff, log g and M/H for 292 M dwarfs of spectral type M0 to M9, where the formation of dust and clouds are important. The derived Teff for the sample ranges from 2300 to 4000 K, values of log g ranges from 4.5 ≤ logg ≤ 5.5 and the resulting metallicity ranges from −0.5 ≤ M/H ≤ +0.5. We have also explored the possible differences in Teff, log g and M/H by comparing them with other studies of the same sample of M dwarfs.
Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. Their application is, however, limited by the voltage decay upon cycling, and the origin of ...such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 to 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. This discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.
The first part of this study documented the as-aged microstructure of five cast aluminum alloys namely, 206, 319, 356, A356, and A356+0.5Cu, that are used for manufacturing automotive cylinder heads ...(Roy
et al.
in Metall Mater Trans A,
2016
). In the present part, we report the mechanical response of these alloys after they have been subjected to various levels of thermal exposure. In addition, the thermophysical properties of these alloys are also reported over a wide temperature range. The hardness variation due to extended thermal exposure is related to the evolution of the nano-scale strengthening precipitates for different alloy systems (Al-Cu, Al-Si-Cu, and Al-Si). The effect of strengthening precipitates (size and number density) on the mechanical response is most obvious in the as-aged condition, which is quantitatively demonstrated by implementing a strength model. Significant coarsening of precipitates from long-term heat treatment removes the strengthening efficiency of the nano-scale precipitates for all these alloys systems. Thermal conductivity of the alloys evolve in an inverse manner with precipitate coarsening compared to the strength, and the implications of the same for the durability of cylinder heads are noted.
In order to investigate the near wing of the Lyman-
α
line, accurate line profile calculations and molecular data are both required due to the existence of a close line satellite responsible for its ...asymmetrical shape. Lyman-
α
lines observed with the Cosmic Origin Spectograph on the
Hubble
Space Telescope show this peculiarity in the spectra of DBA and DA white dwarf stars. A similar asymmetrical shape in the blue wing can be predicted in the Balmer-
α
line of H perturbed by He and H atoms. In continuation with a very recent work on the Lyman-
α
line, where the
n
= 2 potential energies and transition dipole moments from the ground state were determined, we present new accurate H-He potential energies and electronic transition dipole moments involving the molecular states correlated with H(
n
= 3)+He and their transition dipole moments with the states correlated with H(
n
= 2)+He. Those new data and existing molecular data for H(
n
= 2,3)-H are used to provide a theoretical investigation of the collisional effects in the blue wing of the Balmer-
α
line of H perturbed by He and H atoms. We note the consequences for the Balmer-
α
line shape in the physical conditions found in the cool atmosphere of DZA white dwarfs where helium densities may be as high as 10
21
cm
−3
. This study is undertaken with a unified theory of spectral line broadening valid at very high helium densities.
Sirius has always attracted a lot of scientific interest, especially after the discovery of a companion white dwarf at the end of the 19th century. Very early on, the existence of a potential third ...body was put forward to explain some of the observed properties of the system. We present new coronagraphic observations obtained with VLT/SPHERE (Very Large Telescope/Spectro-Polarimetric High-contrast Exoplanet REsearch) that explore, for the very first time, the innermost regions of the system down to 0.2 arcsec(0.5 au) from Sirius A. Our observations cover the near-infrared from 0.95 to 2.3 μm and they offer the best on-sky contrast ever reached at these angular separations. After detailing the steps of our SPHERE/IRDIFS data analysis, we present a robust method to derive detection limits for multispectral data from high-contrast imagers and spectrographs. In terms of raw performance, we report contrasts of 14.3 mag at 0.2 arcsec, ∼16.3 mag in the 0.4–1.0 arcsec range and down to 19 mag at 3.7 arcsec. In physical units, our observations are sensitive to giant planets down to 11 M
Jup at 0.5 au, 6–7 M
Jup in the 1–2 au range and ∼4 M
Jup at 10 au. Despite the exceptional sensitivity of our observations, we do not report the detection of additional companions around Sirius A. Using a Monte Carlo orbital analysis, we show that we can reject, with about 50 per cent probability, the existence of an 8 M
Jup planet orbiting at 1 au.
We present evolutionary models for cool brown dwarfs and extra-solar giant planets. The models reproduce the main trends of observed methane dwarfs in near-IR color-magnitude diagrams. We also ...present evolutionary models for irradiated planets, coupling for the first time irradiated atmosphere profiles and inner structures. We focus on HD 209458-like systems and show that irradiation effects can substantially affect the radius of sub-jovian mass giant planets. Irradiation effects, however, cannot alone explain the large observed radius of HD 209458b. Adopting assumptions which optimise irradiation effects and taking into account the extension of the outer atmospheric layers, we still find ~20% discrepancy between observed and theoretical radii. An extra source of energy seems to be required to explain the observed value of the first transit planet.
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