By using the strategy of pre-assembly chlorosulfonation applied to a linker precursor, the first sulfonated zirconium metal–organic framework ( JUK-14 ) with two-dimensional (2D) structure, was synthesized. Single-crystal X-ray diffraction reveals that the material is built of Zr6O4(OH)4(COO)8 oxoclusters, doubly 4-connected by angular dicarboxylates, and stacked in layers spaced 1.5 nm apart by the presence of sulfonic groups. JUK-14 exhibits excellent hydrothermal stability, permanent porosity confirmed by gas adsorption studies, and shows high (>10−4 S/cm) and low (<10−8 S/cm) proton conductivity under humidified and anhydrous conditions, respectively. Post-synthesis inclusion of imidazole improves the overall conductivity increasing it to 1.7×10−3 S/cm at 60 °C and 90 % relative humidity, and by 3 orders of magnitude at 160 °C. The combination of 2D porous nature with robustness of zirconium MOFs offers new opportunities for exploration of the material towards energy and environmental applications. 相似文献
In this paper we give necessary and sufficient conditions for blow-up of solutions for a particular class of nonlinear Volterra equations. We also give some examples. 相似文献
The surface morphology and thermal properties of polyurethanes can be correlated to their chemical composition. The hydrophilicity, surface morphology, and thermal properties of polyurethanes (differed in soft segments and in linear/cross-linked structure) were investigated. The influence of poly([R,S]-3-hydroxybutyrate) presence in soft segments and blending of polyurethane with polylactide on surface topography were also estimated. The linear polyurethanes (partially crystalline) had the granular surface, whereas the surface of cross-linked polyurethanes (almost amorphous) was smooth. Round aggregates of polylactide un-uniformly distributed in matrix of polyurethane were clearly visible. It was concluded that some modification of soft segment (by mixing of poly([R,S]-3-hydroxybutyrate) with different polydiols and polytriol) and blending of polyurethanes with small amount of polylactide influence on crystallinity and surface topography of obtained polyurethanes. 相似文献
The problem of the estimating of a blow-up time for solutions of Volterra nonlinear integral equation with convolution kernel is studied. New estimates, lower and upper, are found and, moreover, the procedure for the improvement of the lower estimate is presented. Main results are illustrated by examples. The new estimates are also compared with some earlier ones related to a shear band model. 相似文献
We consider an initial‐boundary value problem for nonstationary Stokes system in a bounded domain Omega??3 with slip boundary conditions. We assume that Ω is crossed by an axis L. Let us introduce the following weighted Sobolev spaces with finite norms: and where ?(x) = dist{x, L}. We proved the result. Given the external force f∈L2, ?µ(ΩT), initial velocity v0∈H(Ω), µ∈?+\? there exist velocity v∈H(ΩT) and the pressure p, ?p∈L2, ?µ(ΩT) and a constant c, independent of v, p, f, such that As we consider the Stokes system in weighted Sobolev spaces the following two things must be used:
The ultrafast relaxation of aqueous iron(II)-tris(bipyridine) upon excitation into the singlet metal-to-ligand charge-transfer band (1MLCT) has been characterized by femtosecond fluorescence up-conversion and transient absorption (TA) studies. The fluorescence experiment shows a very short-lived broad 1MLCT emission band at approximately 600 nm, which decays in < or =20 fs, and a weak emission at approximately 660 nm, which we attribute to the 3MLCT, populated by intersystem crossing (ISC) from the 1MLCT state. The TA studies show a short-lived (<150 fs) excited-state absorption (ESA) below 400 nm, and a longer-lived one above 550 nm, along with the ground-state bleach (GSB). We identify the short-lived ESA as being due to the 3MLCT state. The long-lived ESA decay and the GSB recovery occur on the time scale of the lowest excited high-spin quintet state 5T2 lifetime. A singular value decomposition and a global analysis of the TA data, based on a sequential relaxation model, reveal three characteristic time scales: 120 fs, 960 fs, and 665 ps. The first is the decay of the 3MLCT, the second is identified as the population time of the 5T2 state, while the third is its decay time to the ground state. The anomalously high ISC rate is identical in [RuII(bpy)3]2+ and is therefore independent of the spin-orbit constant of the metal atom. To reconcile these rates with the regular quasi-harmonic vibrational progression of the 1MLCT absorption, we propose a simple model of avoided crossings between singlet and triplet potential curves, induced by the strong spin-orbit interaction. The subsequent relaxation steps down to the 5T2 state dissipate approximately 2000 cm-1/100 fs. This rate is discussed, and we conclude that it nevertheless can be described by the Fermi golden rule, despite its high value. 相似文献
We define a natural ensemble of trace preserving, completely positive quantum maps and present algorithms to generate them at random. Spectral properties of the superoperator Φ associated with a given quantum map are investigated and a quantum analogue of the Frobenius-Perron theorem is proved. We derive a general formula for the density of eigenvalues of Φ and show the connection with the Ginibre ensemble of real non-symmetric random matrices. Numerical investigations of the spectral gap imply that a generic state of the system iterated several times by a fixed generic map converges exponentially to an invariant state. 相似文献
We consider a random walk which is obtained from the simple random walk by a discrete time version of Bochner’s subordination. We prove that under certain conditions on the subordinator appropriately scaled random walk converges in the Skorohod space to the symmetric -stable process . We also prove asymptotic formula for the transition function of similar to the Pólya’s asymptotic formula for . 相似文献
Present work describes investigations of a two-step process consisting of galvanostatic anodising in a 1 M H2SO4 solution at 100 mA cm−2 up to the limiting voltages of 20, 60, 80, 100 and 120 V, directly after which potentiostatic regime was employed and the current was allowed to drop. The total treatment time (5 min) was held constant for all samples. The treatment was carried out to improve the corrosion resistance of zirconium in physiological conditions, which was determined by electrochemical evaluation in Ringer’s solution. XPS studies revealed that after anodising sulphur was incorporated into the oxide film in the form of sulphated zirconia. The maximum content of sulphate in the oxide layer was observed after anodising at 80 V. Anodising at higher voltages resulted in formation of coatings with decreasing amount of sulphur. It was found that there is a strong correlation between the sulphur content in the oxide layers and the measured corrosion current density. On the other hand, the pitting corrosion resistance seemed to be unaffected by the presence of S and it was improving with the increasing limiting voltage of the treatment.
The title compound, C11H16O2, adopts a semifolded conformation with the δ‐lactone and cyclohexane rings almost perpendicular to one another. The β‐methyl substituent occupies an axial position with respect to the cyclohexane ring. The δ‐lactone moiety adopts a slightly distorted half‐chair arrangement, while the cyclohexane ring exists in an almost ideal chair conformation. 相似文献