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Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural with ALD overcoating (II) – Comparison between TiO2 and Al2O3 overcoatings
TiO2 atomic layer deposition (ALD) overcoatings were applied to copper chromite catalysts to increase the stability for 2-furfuraldehyde (“furfural”) hydrogenation. After overcoating, about 75% activity was preserved compared to neat copper chromite: much higher activity than an alumina ALD overcoated catalyst with a similar number of ALD cycles. The effects of ALD TiO2 on the active Cu nanoparticles were studied extensively using both in-situ TPR/isothermal-oxidation and in-situ furfural hydrogenation via Cu XAFS. The redox properties of Cu were modified only slightly by the TiO2 ALD overcoat. However, a subtle electronic interaction was observed between the TiO2 ALD layers and the Cu nanoparticles. With calcination at 500 °C the interaction between the TiO2 overcoat and the underlying catalyst is strong enough to inhibit migration and site blocking by chromite, but is sufficiently weaker than the interaction between the Al2O3 overcoat and copper chromite that it does not strongly inhibit the catalytic activity of the copper nanoparticles.
X-ray cavities in a sample of 83 SPT-selected clusters of galaxies: Tracing the evolution of AGN feedback in clusters of galaxies out to z = 1.2
X-ray cavities are key tracers of mechanical (or radio mode) heating arising from the active galactic nuclei (AGNs) in brightest cluster galaxies (BCGs). We report on a survey for X-ray cavities in 83 massive, high-redshift (0.4 7 Gyr at z∼0.8). On average, the detected X-ray cavities have powers of (0.8−5)×10{sup 45} erg s{sup −1}, enthalpies of (3−6)×10{sup 59} erg, and radii of ∼17 kpc. Integrating over 7 Gyr, we find that the supermassive black holes in BCGs may have accreted 10{sup 8} to several 10{sup 9} M{sub ⊙} of material to power these outflows. This level of accretion indicates that significant supermassive black hole growth may occur not only at early times, in the quasar era, but at late times as well. We also find that X-ray cavities at high redshift may inject an excess heat of 0.1–1.0 keV per particle into the hot ICM above and beyond the energy needed to offset cooling. Although this result needs to be confirmed, we note that the magnitude of excess heating is similar to the energy needed to preheat clusters, break self-similarity, and explain the excess entropy in hot atmospheres.
Hybrid Ultra‐Microporous Materials for Selective Xenon Adsorption and Separation
Abstract The demand for Xe/Kr separation continues to grow due to the industrial significance of high‐purity Xe gas. Current separation processes rely on energy intensive cryogenic distillation. Therefore, less energy intensive alternatives, such as physisorptive separation, using porous materials, are required. Herein we show that an underexplored class of porous materials called hybrid ultra‐microporous materials (HUMs) affords new benchmark selectivity for Xe separation from Xe/Kr mixtures. The isostructural materials, CROFOUR‐1‐Ni and CROFOUR‐2‐Ni, are coordination networks that have coordinatively saturated metal centers and two distinct types of micropores, one of which is lined by CrO 4 2− (CROFOUR) anions and the other is decorated by the functionalized organic linker. These nets offer unprecedented selectivity towards Xe. Modelling indicates that the selectivity of these nets is tailored by synergy between the pore size and the strong electrostatics afforded by the CrO 4 2− anions.
Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal–Organic Framework
The cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal organic frameworks containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid state adsorbents but no experimental insights on the nature of the Xe-network interaction is available to date. Here we report a new microporous metal organic framework (designated SBU2) that is selective toward Xe over Kr at ambient conditions, with Xe/Kr selectivity of about 10 and Xe capacity of 37.1 wt% at 298 K. Results of single crystal diffraction show Xe selectivity may be attributed to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both serving as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBU2 was investigated with experimental and computational breakthrough methods. These experiments showed that Xe broke through the column after 3 min, followed by Kr at 4.5 min after injection of gases mixture, which confirmed that SBU2 has a real practical potential for separating Xe from Kr. Computational calculations show that SBU2 capacity and adsorption selectivity is comparable to the best-performing unmodified MOFs such as Ni-MOF-74 or Co Formate.
Influence of single particle orbital sets and configuration selection on multideterminant wavefunctions in quantum Monte Carlo
Multideterminant wavefunctions, while having a long history in quantum chemistry, are increasingly being used in highly accurate quantum Monte Carlo calculations. Since the accuracy of QMC is ultimately limited by the quality of the trial wavefunction, multi-Slater determinants wavefunctions offer an attractive alternative to Slater-Jastrow and more sophisticated wavefunction ansatz for several reasons. They can be efficiently calculated, straightforwardly optimized, and systematically improved by increasing the number of included determinants. In spite of their potential, however, the convergence properties of multi-Slater determinant wavefunctions with respect to orbital set choice and excited determinant selection are poorly understood, which hinders the application of these wavefunctions to large systems and solids. In this paper, by performing QMC calculations on the equilibrium and stretched carbon dimer, we find that convergence of the recovered correlation energy with respect to number of determinants can depend quite strongly on basis set and determinant selection methods, especially where there is strong correlation. We demonstrate that properly chosen orbital sets and determinant selection techniques from quantum chemistry methods can dramatically reduce the required number of determinants (and thus the computational cost) to reach a given accuracy, which we argue shows clear need for an automatic QMC-only method for selecting determinants and generating optimal orbital sets.
Tuning the Solid Electrolyte Interphase for Selective Li‐ and Na‐Ion Storage in Hard Carbon
Solid‐electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li‐ and Na‐ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li‐ or Na‐based electrolyte, and that ionic transport can be kinetically controlled. Selective Li‐ and Na‐based SEI membranes are produced using Li‐ or Na‐based electrolytes, respectively. The Na‐based SEI allows easy transport of Li ions, while the Li‐based SEI shuts off Na‐ion transport. Na‐ion storage can be manipulated by tuning the SEI layer with film‐forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g −1 ; ≈ 1/10 of the normal capacity (250 mAh g −1 ). Unusual selective/preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion‐selective conductors using electrochemical approaches.
Synthesis of Two-Dimensional Materials by Selective Extraction
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Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen
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Increasing the Aromatic Selectivity of Quinoline Hydrogenolysis Using Pd/MOx–Al2O3
Catalysts consisting of Pd nanoparticles supported on highly dispersed TiOx–Al2O3, TaOx–Al2O3, and MoOx–Al2O3 are studied for catalytic quinoline hydrogenation and selective C–N bond cleavage at 275 °C and 20 bar H2. The Pd/MOx–Al2O3 materials exhibit significantly greater aromatic product selectivity and thus 10–15 % less required H2 for a given level of denitrogenation relative to an unmodified Pd/Al2O3 catalyst.
Selective Monooxidation of Light Alkanes Using Chloride and Iodate
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“Supersaturated” Self-Assembled Charge-Selective Interfacial Layers for Organic Solar Cells
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Kinetic and structural studies, origins of selectivity, and interfacial charge transfer in the artificial photosynthesis of CO
The effective design of an artificial photosynthetic system entails the optimization of several important interactions. Herein we report stopped-flow UV-Vis spectroscopy, X-ray crystallography, DFT, and electrochemical kinetic studies of the Re(bipy-tBu)(CO)3(L) catalyst system. A remarkable selectivity for CO2 over H+ was observed by stopped-flow UV-Vis spectroscopy of [Re(bipy-tBu)(CO)3]-. The pseudo-first order rate constant for the reaction with 10 mM CO2 in THF is 35 s-1. This is ca. 15-20 times faster than the reactions with water or methanol at the same concentration in THF. X-ray crystallography and DFT studies of the doubly-reduced anionic species suggest that the HOMO has mixed metal-ligand character rather than being purely dz 2, which is thought to aid catalytic selectivity by favoring binding of CO2 over H+. Electrocatalytic studies performed with the addition of Brönsted acids reveal a primary H/D kinetic isotope effect, indicating that transfer of protons to Re-CO2 is involved in the rate limiting step. Lastly, the effects of electrode surface modification on interfacial electron transfer between a semiconductor and catalyst were investigated and found to affect the observed catalytic rates up to seven-fold, indicating that the properties of the electrode surface should not be overlooked when developing a homogeneous artificial photosynthetic system. This research was supported at the University of Washington, Seattle by the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry (for a fellowship to A. J. M. M.), and, for funds to purchase the stopped-flow instrument, the U.S. National Institutes of Health 13 (Grant GM-50422 to JMM), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.
Temperature-dependent selective oxidation processes for Ni-5Cr and Ni-4Al
The selective oxidation of Ni-5Cr and Ni-4Al alloys is evaluated during high (800°C) and low (420°C) temperature exposures with the oxygen partial pressure moderated by a Ni/NiO powder buffer. Internal oxidation of Cr and Al is observed throughout the matrix and at grain boundaries at 800°C accompanied by the ejection of Ni onto the surface for both. At 420°C, matrix internal oxidation was eliminated and only Ni-4Al exhibited intergranular (IG) oxidation. Surprisingly, a protective surface oxide rapidly formed for Ni-5Cr blocking IG oxidation. This is contradictory to results in 330–360°C hydrogenated water environments where both alloys show IG oxidation.
Enhanced Thermal Stability of W-Ni-Al 2 O 3 Cermet-Based Spectrally Selective Solar Absorbers with Tungsten Infrared Reflectors
Solar thermal technologies such as solar hot water and concentrated solar power trough systems rely on spectrally selective solar absorbers. These solar absorbers are designed to efficiently absorb the sunlight while suppressing re-emission of infrared radiation at elevated temperatures. Efforts for the development of such solar absorbers must not only be devoted to their spectral selectivity but also to their thermal stability for high temperature applications. In this work, selective solar absorbers based on two cermet layers are fabricated on mechanically polished stainless steel substrates using a magnetron sputtering technique. The targeted operating temperature is 500–600 °C. A detrimental change in the morphology, phase, and optical properties is observed if the cermet layers are deposited on a stainless steel substrate with a thin nickel adhesion layer, which is due to the diffusion of iron atoms from the stainless steel into the cermet layer forming a FeWO 4 phase. In order to improve thermal stability and reduce the infrared emittance, tungsten is found to be a good candidate for the infrared reflector layer due to its excellent thermal stability and low infrared emittance. Lastly, a stable solar absorptance of ≈0.90 is demonstrated, with a total hemispherical emittance of 0.15 at 500 °C.
Hydrophobic pillared square grids for selective removal of CO 2 from simulated flue gas
Capture of CO2 from flue gas is considered to be a feasible approach to mitigate the effects of anthropogenic emission of CO2. Herein we report that an isostructural family of metal organic materials (MOMs) of general formula [M(linker)(2)(pillar)], linker = pyrazine, pillar = hexaflourosilicate and M = Zn, Cu, Ni and Co exhibits highly selective removal of CO2 fromdry and wet simulated flue gas. Two members of the family, M = Ni and Co, SIFSIX-3-Ni and SIFSIX-3-Co, respectively, are reported for the first time and compared with the previously reported Zn and Cu analogs.
Galaxies in X-Ray Selected Clusters and Groups in Dark Energy Survey Data. I. Stellar Mass Growth of Bright Central Galaxies Since z ~ 1.2
Using the science verification data of the Dark Energy Survey for a new sample of 106 X-ray selected clusters and groups, we study the stellar mass growth of bright central galaxies (BCGs) since redshift z ~ 1.2. Compared with the expectation in a semi-analytical model applied to the Millennium Simulation, the observed BCGs become under-massive/under-luminous with decreasing redshift. Here, we incorporate the uncertainties associated with cluster mass, redshift, and BCG stellar mass measurements into an analysis of a redshift-dependent BCG-cluster mass relation, $m_*$ $∝ \huge{(}$$\frac{M_{200}}{1.5x10^{14}M_⊙}\huge{)}$$^{0.24±0.08}$ $(1 + z)$$^{-0.19±0.34}$, and compare the observed relation to the model prediction. We estimate the average growth rate since z = 1.0 for BCGs hosted by clusters of M 200,z = 10 13.8 M ⊙ ; at z = 1.0: m * , BCG appears to have grown by 0.13 ± 0.11 dex, in tension at the ~2.5σ significance level with the 0.40 dex growth rate expected from the semi-analytic model. We show that the build-up of extended intracluster light after z = 1.0 may alleviate this tension in BCG growth rates.