Hysteretic adsorption

Zhao, X., Bo. Xiao, A.J. Fletcher, K.M. Thomas, D. Bradshaw, M.J. Rosseinsky, Hysteretic adsorption and desorption of hydrogen by nanoporous metal-organic frameworks. Science 306,1012,2004. 

Canonical ensemble density functional theory (CEDFT) has been employed for predicting hysteretic adsorption/desorption isotherms in nanopores of different geometries in the wide range of pore sizes (1 - 12 nm). It is shown that the CEDFT model qualitatively describes equilibrium and spinodal transitions and is in a reasonable quantitative agreement with experiments on well-characterized MCM-41 samples. A DFT-based method for calculating pore size distributions from the adsorption and desorption branches of nitrogen adsorption isotherms has been elaborated and tested against literature data on capillary condensation in MCM-41 samples with pores from 5 to 10 nm. 

Structural change without bond breaking occurs with a scissoring motion leading to an increase in crystallographic cell volume of ethanol and methanol templated phases E and M of Ni2(bpy)3.(N03)4 during adsorption of the templates. Hysteretic adsorption was observed... 

To examine the dynamical aspect of the hysteretic behavior, we consider the system geometry shown in Fig. 4. The porous material of length L in the z-direction is bounded by the gas reservoirs at z = 0 and z = L. Periodic boundary conditions are imposed on the X and y-directions. In typical experimental situations, starting from a (quasi)-equilibrium state, the external vapor pressure of the gas reservoir is instantaneously changed by a small amount, which induces gradual relaxations of the system into a new state. This geometry was used in recent work on dynamics of off-lattice models of adsorption (Sarkisov and Monson,... 

Earlier, we have made the following general conclusions regarding the capillary condensation in cylindrical pores [7], The reversible isotherms in sufficiently narrow pores and the desorption branches of hysteretic isotherms in wider pores correspond to the equilibrium transitions predicted by the NLDFT. The adsorption branches of hysteretic isotherms lie inside the theoretical hysteresis loop. The metastable states on the theoretical desorption branch are not observed. These conclusions were made based on analyses of limited experimental data on reference MCM-41 materials with pores of diameter < 5nm. Sayari et al. [8-10] have recently synthesized enlarged MCM-41 samples with pore diameters from 5 to 10 nm. The Nj isotherms on these samples are presented in Figs. 3-6 in comparison with the theoretical loops for cylindrical pores of average size, formed by the metastable adsorption branch and the equilibrium desorption branch. The experimental and theoretical hysteresis loops are in a perfect qualitative agreement. 

The electrochemical transients, hysteretic T -i, rising ir-t and decreasing T -t may be simply and quantitatively explained in terms of disruption and displacement of the rapidly formed PEG-CI blocking layer by the more gradual adsorption and formation of the catalytic SPS-C1 species [12, 62, 66, 67, 136, 243, 264, 268, 269]. Additional complications arise when considering nucleation of copper on a foreign substrate [270, 271]. 

View of the structures of [Ni2(N03)4(4,4 -bipyridine)3]. (a) View of the T-shaped connectivity adopted by the Ni(N03>2 unit leading to decorated one-dimensional chains within two-dimensional bilayer structures as observed in compound (E). View of the ladder structures as observed in compound (M). (b) Hysteretic H2 adsorption-desorption at 77 K. (Zhao et ai, 2004. Reprinted with permission from AAAS). 

When fillers and rubbers are dry mixed and the resulting samples solvent extracted, the amount of rubber bound is clearly the result of all possible adsorption mechanisms as well as of intermolecular cross-linking. Because of the hysteretic nature of physical adsorption, chemical interactions are not necessary for the development of some bound rubber. In many cases, however, chemisorption aixl grafting dominate the physical adsorption. Sircar and Voet (97) used low molecular weight SBR and polyisobutylenes 50,000 and less) to minimize the... 

The dehydrated MIL-53 compounds have moderate H2 adsorption capacities of 2.8 wt% for MIL-53(Cr) and 3.8 wt% for MIL-53 (Al) [131]. Significant adsorp-tion/desorption hysteretic behaviour was observed in the H2 isotherm which is clearly due to the dynamic behaviour of MIL-53. 

Fig. 13 (a) Multi-steps N2 isotherms and (b) high pressure hysteretic H2 adsorption-desorption in [Co(BDP)] [153], Reproduced by kind permission of the authors... 

An example of this approach is represented by the growth of 3-D coordination polymers with SCO properties via stepwise adsorption reactions for multilayer films based entirely on intra- and interlayer coordination bonds Fe(pyrazine) [Pt(CN) ] [218, 219], Indeed, after functionalization of the surface with the appropriate anchoring layer the coordination polymer is built in a stepwise fashion, alternating the metal ion (Fe "), the platinum salt ([Pt(CN) ] ), and pyrazine. The polymer shows many interesting properties, with the SCO transition accompanied by a variation in the dielectric constant of the material accompanied by a room temperature hysteresis of the dielectric constants. This dielectric hysteretic property may be useful in building molecular memory devices that can store information by high- and low-capacitance states. What must be remarked here is that these appealing properties cannot be exploited in bulk materials, but only in thin films. 

Random-distribution solution SBR vulcanizates are less hysteretic than are comparable vulcanizates of E-SBR. Also, solution polymers contain less nonrubber material. This is because there is absence of emulsifier (e.g., soap) during polymerization. During coagulation of the polymerized emulsion to obtain the rubber, fatty acids are formed. The presence of such fatty acid, in part, reduces the rate of vulcanization with respect to that of solution SBR compounds. The absence of such nonrubber components also reduces the electrical conductivity of S-SBR compounds compared to those of E-SBR. Vulcanizates of solution SBRs, having blocky monomer distributions, have very low brittleness temperatures due to the presence of relatively long polybutadiene chain segments. They have good elastic properties, low water adsorption, low electrical conductivity, and excellent abrasion resistance. 

In this umtk, we aim at j dning insists at a molecular level on the hysteretic behavior of adsorption/desorption isoftienns of several fluids rxinfined in a rather large collection of pore models tlut include sin e pores of varioiui gennetries (cylinders, ellipsoids, constricted pores and Vycor). 

Another approach to metallation of a MOF is to chemically reduce a neutral MOF with concomitant cation uptake to balance the charge, which has been pursued by FIupp and coworkers. " Remarkably, reduction of the twofold interpenetrating MOF [Zn2(ndc)2(dipyni)] (ndc = 2,6-napthalenedicarboxylate dipyni = A,M-di-(4-pyridyl)-1,4,5,8-napthalenetetracarboxydiimide) can be achieved by direct reaction with Li(0) in DMF. H2 uptake is enhanced at an optimal Li(I) loading of 5 mol%, and the hydrogen adsorption and desorption profile is hysteretic indicative of dynamic framework behavior. Such dynamic behavior was not observed in the unmetalled MOF. This MOF can also... 

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