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The quantum kinetic molecular sieving and the various surface interactions that are observed during the adsorption of [H.sub.2] and [D.sub.2] on a mixed metal-organic framework material are discussed. The adsorption kinetics is shown to be faster for the [D.sub.2] complex, as compared to that for [H.sub.2].

Polyethylene oxide (PEO) has been widely used in biomedical fields. The antibiofouling property of the PEO-modified surface has been extensively investigated but is far from being fully understood. A series of PEOs with narrowly distributed molecular weight (Mw), synthesized with the technique of high vacuum anionic polymerization, have been successfully grafted onto the surface of silicon wafers. The power-law relationship between the thickness of the monolayer versus the Mw of the grafted PEO shows a scaling of 0.3, indicating compact condensing of the chains. The static contact angles show higher hydrophobicity for the layer of PEO with higher Mw, which can be attributed to the closely packed conformation of the chains with high density. The frequency shift of the contact resonance indicates that the Young's modulus decreases and the loss factor increases with the increase in the Mw of PEO and the thickness of the PEO layers. Dielectric spectroscopy of bare or PEO-grafted wafers in the aqueous solutions reveals an interfacial polarization, which results from compositional and structural changes in the interface layer and depends on temperatures and salt concentrations. At a given grafting density, the PEO chains are swollen in pure water, demonstrating hydrophilic behavior, whereas they collapse in salt solutions, showing hydrophobic characteristics. [ABSTRACT FROM AUTHOR]

Dynamic arrest transitions of colloidal suspensions containing nonspherical particles are of interest for the design and processing of various particle technologies. To better understand the effects of particle shape anisotropy and attraction strength on gel and glass formation, we present a colloidal model system of octadecyl-coated silica rods, termed as adhesive hard rods (AHR), which enables control of rod aspect ratio and temperature-dependent interactions. The aspect ratios of silica rods were controlled by varying the initial TEOS concentration following the work of Kuijk et al. (J. Am. Chem. Soc., 2011, 133, 2346-2349) and temperature-dependent attractions were introduced by coating the calcined silica rods with an octadecyl-brush and suspending in tetradecane. The rod length and aspect ratio were found to increase with TEOS concentration as expected, while other properties such as the rod diameter, coating coverage, density, and surface roughness were nearly independent of the aspect ratio. Ultrasmall angle X-ray scattering measurements revealed temperature-dependent attractions between octadecyl-coated silica rods in tetradecane, as characterized by a low-q upturn in the scattered intensity upon thermal quenching. Lastly, the rheology of a concentrated AHR suspension in tetradecane demonstrated thermoreversible gelation behavior, displaying a nearly 5 orders of magnitude change in the dynamic moduli as the temperature was cycled between 15 and 40 °C. The adhesive hard rod model system serves as a tunable platform to explore the combined influence of particle shape anisotropy and attraction strength on the dynamic arrest transitions in colloidal suspensions with thermoreversible, short-range attractions. [ABSTRACT FROM AUTHOR]

Lithium-ion-conducting solid electrolytes hold promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic conductivity and a broad electrochemical window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of the room-temperature lithium-ion conductivity by 3 orders of magnitude through the creation of nanostructured Li3PS4. This material has a wide electrochemical window (5 V) and superior chemical stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance the ionic conductivity: (1) the reduction of the dimensions to a nanometer-sized framework stabilizes the high-conduction β phase that occurs at elevated temperatures, and (2) the high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic conductivity of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications, including batteries, fuel cells, sensors, photovoltaic systems, and so forth. [ABSTRACT FROM AUTHOR]

A rational strategy has been used to immobilize open metal sites in ultramicroporosity for stronger binding of multiple H2 molecules per unsaturated metal site for H2 storage applications. The synthesis and structure of a mixed zinc/copper metal-organic framework material Zn3(BDC)3[Cu(Pyen)] •(DMF)5(H2O)5 (H2BDC = 1,4 benzenedicarboxylic acid and PyenH2 = 5-methyl-4-oxo-1,4-dihydro-pyridine-3-carbaldehyde) is reported. Desolvation provides a bimodal porous structure Zn3(BDC)3[Cu(Pyen)] (M′MOF 1) with narrow porosity (<0.56 nm) and an array of pores in the bccrystallographic plane where the adsorbate-adsorbent interactions are maximized by both the presence of open copper centers and overlap of the potential energy fields from pore walls. The H2 and D2 adsorption isotherms for M′MOF 1 at 77.3 and 87.3 K were reversible with virtually no hysteresis. Methods for determination of the isosteric enthalpies of H2 and D2 adsorption were compared. A virial model gave the best agreement (average deviation <1 standard deviation) with the isotherm data. This was used in conjunction with the van't Hoff isochore giving isosteric enthalpies at zero surface coverage of 12.29 ± 0.53 and 12.44 ± 0.50 kJ mol-1 for H2 and D2 adsorption, respectively. This is the highest value so far observed for hydrogen adsorption on a porous material. The enthalpy of adsorption, decreases with increasing amount adsorbed to 9.5 kJ mol-1 at ~1 .9 mmol g-1 (2 H2 or D2 molecules per Cu corresponding to adsorption on both sides of planar Cu open centers) and is virtually unchanged in the range 1.9-3.6 mmol g-1. Virial analysis of isotherms at 87.3 K is also consistent with two H2 or D2 molecules being bound to each open Cu center. The adsorption kinetics follow a double exponential model, corresponding to diffusion along two types of pores, a slow component with high activation energy (13.35 ± 0.59 kJ mol-1) for the narrow pores and a faster component with low activation energy (8.56 ± 0.41 kJ mol-1). The D2 adsorption kinetic constants for both components were significantly faster than the corresponding H2 kinetics for specific pressure increments and had slightly lower activation energies than the corresponding values for H2 adsorption. The kD2/kH2 ratio for the slow component was 1.62 ± 0.07, while the fast component was 1.38 ± 0.04 at 77.3 K, and the corresponding ratios were smaller at 87.3 K. These observations of kinetic isotope quantum molecular sieving in porous materials are due to the larger zero-point energy for the lighter H2, resulting in slower adsorption kinetics compared with the heavier D2. The results show that a combination of open metal centers and confinement in ultramicroporosity leads to a high enthalpy for H2 adsorption over a wide range of surface coverage and quantum effects influence diffusion of H2 and D2 in pores in M′MOF 1. [ABSTRACT FROM AUTHOR]