H2 storage in isostructural UiO-67 and UiO-66 MOFs

The recently discovered UiO-66/67/68 class of isostructural metallorganic frameworks (MOFs) [J. H. Cavka et al. J. Am. Chem. Soc., 2008, 130, 13850] has attracted great interest because of its remarkable stability at high temperatures, high pressures and in the presence of different solvents, acids and bases [L. Valenzano et al. Chem. Mater., 2011, 23, 1700]. UiO-66 is obtained by connecting Zr(6)O(4)(OH)(4) inorganic cornerstones with 1,4-benzene-dicarboxylate (BDC) as linker resulting in a cubic MOF, which has already been successfully reproduced in several laboratories. Here we report the first complete structural, vibrational and electronic characterization of the isostructural UiO-67 material, obtained using the longer 4,4'-biphenyl-dicarboxylate (BPDC) linker, by combining laboratory XRPD, Zr K-edge EXAFS, TGA, FTIR, and UV-Vis studies. Comparison between experimental and periodic calculations performed at the B3LYP level of theory allows a full understanding of the structural, vibrational and electronic properties of the material. Both materials have been tested for molecular hydrogen storage at high pressures and at liquid nitrogen temperature. In this regard, the use of a longer ligand has a double benefit: (i) it reduces the density of the material and (ii) it increases the Langmuir surface area from 1281 to 2483 m(2) g(-1) and the micropore volume from 0.43 to 0.85 cm(3) g(-1). As a consequence, the H(2) uptake at 38 bar and 77 K increases from 2.4 mass% for UiO-66 up to 4.6 mass% for the new UiO-67 material. This value is among the highest values reported so far but is lower than those reported for MIL-101, IRMOF-20 and MOF-177 under similar pressure and temperature conditions (6.1, 6.2 and 7.0 mass%, respectively) [A. G. Wong-Foy et al. J. Am. Chem. Soc., 2006, 128, 3494; M. Dinca and J. R. Long. Angew. Chem., Int. Ed., 2008, 47, 6766]. Nevertheless the remarkable chemical and thermal stability of UiO-67 and the absence of Cr in its structure would make this material competitive.     

On Gibson functions with connected graphs

A function f: X → Y between topological spaces is said to be a weakly Gibson function if $f(\bar G) \subseteq \overline {f(G)} $ for any open connected set G ? X. We call a function f: X → Y segmentary connected if X is topological vector space and f([a, b]) is connected for every segment [a, b] ? X. We show that if X is a hereditarily Baire space, Y is a metric space, f: X → Y is a Baire-one function and one of the following conditions holds:

1. X is a connected and locally connected space and f is a weakly Gibson function
2. X is an arcwise connected space and f is a Darboux function
3. X is a topological vector space and f is a segmentary connected function, then f has a connected graph.

     

The evolution of the nanoscale dissipative structures in a distribution of defects within the isothermally irradiated f.c.c. crystal

A kinetic model for the influence of external noises such as fluctuations of the vacancies’ generation rate and inhomogeneity of irradiated f.c.c. crystal on the formation of nanoscale modulated dissipative structure in a spatial distribution of vacancies is considered. The generation rate of vacancies all over the sites and a density of their dislocation-type sinks are modelled as independent random uniform stationary fields and with certain defined parameters of fluctuation correlations – spatial and temporal ones. Such stochastic fields can induce a spatial redistribution of vacancies that can lead to their density stationary uniform field or stochastic one. By the average value and correlation functions of these fluctuations, the conditions are determined for interacting fluctuations of the vacancies’ density, under which this homogeneous random field becomes unstable in relation to the stochastic field with a spatially periodic mean distribution of vacancies’ density. For instance, with f.c.c. nickel as a model of the irradiated functional material, the temperature dependence of spatial period d(T) of the modulated dissipative structure of vacancies’ subsystem in f.c.c. crystal is numerically forecasted and analysed, taking into account the total (‘electrochemical’?+?‘strain-induced’) interaction between vacancies. Such d(T)-dependence is also determined by the kinetic characteristics of vacancies’ redistribution.     

Binding studies of molecular linkers to ZnO and MgZnO nanotip films

Two bifunctional linkers, a rigid-rod p-ethynyl-isophthalic acid capped with a Ru(II)-polypyridyl complex and 3-mercaptopropionic acid, were covalently bound to ZnO nanotip films grown by metal-organic chemical vapor deposition (MOCVD) technology. This highly vertically aligned, crystalline form of ZnO had not been functionalized before. The binding was studied by Fourier transform (FT) IR and UV spectroscopies and probed, in the case of the Ru complex, by static and dynamic fluorescence quenching. The molecules did bind through the carboxylic acid groups, and the FT-IR attenuated total reflectance spectra are indicative of a bidentate carboxylate binding mode. Other molecules (heptanoic acid, isophthalic acid, and trimethoxy(2-phenylethyl)silane) were also bound to the ZnO nanotips. A comparison was made with epitaxial ZnO films grown by MOCVD and ZnO mesoporous films prepared from colloidal solutions to investigate the effect of the ZnO morphology. The ZnO nanotips were excellent binding substrates, particularly for the rigid-rod linker. Since ZnO films are etched at low pH (< 4), novel nanotip films made of ternary MgxZn1-xO, which is formed by alloying ZnO with MgO and is more resistant to acids, were developed. The MgxZn1-xO nanotip films were employed to use linkers with acidic groups and to study the effect of pH pretreatment of the surface on the binding.     

Site affinity effects upon charge injection into siloxane-based monolayers

Submolecular electrical information is successfully derived by applying element-specific, chemically resolved electrical measurements to a covalently bound stilbazole-based monolayer on a silicon substrate. Pronounced affinity effects are found in the response of adjacent atomic sites to external charge injection, accompanied by intramolecular polarization variations. These noncontact electrical read-out capabilities may provide a first entry toward the realization of organic devices based on submolecular electrical units.     

Simple and efficient classification scheme based on specific vocabulary

Assuming a binomial distribution for word occurrence, we propose computing a standardized Z score to define the specific vocabulary of a subset compared to that of the entire corpus. This approach is applied to weight terms (character n-gram, word, stem, lemma or sequence of them) which characterize a document. We then show how these Z score values can be used to derive a simple and efficient categorization scheme. To evaluate this proposition and demonstrate its effectiveness, we develop two experiments. First, the system must categorize speeches given by B. Obama as being either electoral or presidential speech. In a second experiment, sentences are extracted from these speeches and then categorized under the headings electoral or presidential. Based on these evaluations, the proposed classification scheme tends to perform better than a support vector machine model for both experiments, on the one hand, and on the other, shows a better performance level than a Na?ve Bayes classifier on the first test and a slightly lower performance on the second (10-fold cross validation).     

Preparation,structure, and unexpected chemistry of phosphoranyl-derived benziodoxoles

Novel phosphoranyl-derived benziodoxoles were prepared by the reaction of 1-acetoxybenziodoxole with stabilized phosphonium ylides [1-triphenylphosphoranylidene-2-propanone and (carbomethoxymethyl)triphenylphosphoranylidene acetate]. X-ray crystallographic analysis of these compounds demonstrates the significance of secondary bonding interactions, which link individual molecules into infinite chains. An unusual ligand exchange on an iodine(III) center resulting in the substitution of a carbon ligand with an oxygen ligand was observed in the reaction of these compounds with strong acids.     

Graft polymerization from a silica surface initiated by adsorbed peroxide macroinitiators. I. Adsorption and structure of the adsorbed layer of peroxide macroinitiators on a silica surface

The adsorption features of two peroxide macroinitiators (PMIs) with various functionalities from their semi-dilute solutions on the silica surface were thoroughly investigated in the present work. These investigations include the study of the adsorption kinetics of PMI in diverse solvents and a detailed examination of the adsorbed layer structure with the aid of ellipsometry, scanning force microscopy (SFM), and contact angle measurements. Rearrangements of PMI macromolecules at the solid surface are supposed to be the main reason for the appearance of extremes on the kinetic curves and, besides, have a more pronounceable effect on adsorption rate than their diffusion rate to the surface even at the initial stage of the process. Both island-like and densely packed structures of absorbed layers were revealed by combining contact angle measurements and SFM. Surprisingly, even in the case when saturation of the adsorbed layer is reached, PMI does not completely occupy the substrate surface which is at least particularly reachable for the wetting liquids. PMIs adsorbed at the solid surface are intended for the formation of tethered polymer "brushes" via the initiation of "grafting from" polymerization.