GAS SORPTION,DIFFUSION AND PERMEATION OF ORDERED POLYMERIC MEMBRANES

He, CO_2, O_2, N_2, CH_4, C_3H_8, and t-C_4H_(10) gas permeability coefficients and diffusion coefficients of poly(4-methylpentene-1) (PMP) with various degrees of crystallization were plotted against the degree of crystallization. The plotdemonstrated a linear relationship. The gas permeability coefficient and diffusion coefficient of pure amorphous and purecrystalline PMPs were evaluated by a linear extrapolation to zero and 100% crystallinity, respectively. The relationshipbetween the diffusion coefficient of crystalline parts of PMP and the kinetic diameter of penetrant gases was discussed.Syndiotactic polystyrene (SPS) could exist as δ form crystals complexed with organic solvents such as benzene, toluene,xylene, and ethylbenzene. The mesophase of SPS is prepared by annealing the δ form of crystalline complexes at a certaintemperature for 1 h. The desorption of solvent during annealing almost does not result in changes of both the conformation ofbackbone chains and the crystal lattice. We could prepare the mesophase containing molecular cavities with the size andshape of the organic solvent molecules. The mesophase could sorb the same solvent after the manner of Langmuir sorption atlow vapor pressure range while this would not be the case for solvents of different size and shape. This suggests a molecularrecognition of organic solvent, and mesophase SPS might be useful for separation membrane and adsorptive material.

Reactive Alloys of IIA Metals: Gas Sorption and Corrosion as One Process

The present work summarizes the results of previously known, as well as the latest sorption measurements, which were carried out on IIA metal alloys in the form of films, powders and macrobodies with a monolithic structure. Analysis of these data made it possible to construct an empirical sorption model, according to which the corrosive decomposition of reactive alloys is one of the driving forces of the sorption process. This model provides a qualitative description of the sorption behavior of these alloys in a gas environment and can be useful in solving practical problems in the field of vacuum and gas technologies.

Getters Reactants. I. Thermo-Sedimentational Activation

A new method for chemical pumping of gases has been developed using reactive alloys of Li with IIA metals in the liquid state. It is an answer to the need for ultra-high and extremely high vacuum without loose solid particles. Another application of this development is the production of high- and ultra-pure noble gases in a one-step process. Both of these solutions are unprecedented;they are based on a new gas/melt sorption interface that raises the overall bar of technical advances in the field to a higher level, simplifying sorption equipment and leading to cost savings.

Intermetallic Getters Reactants for Vacuum Applications

The present work continues a series of publications devoted to the study of the sorption properties of reactive alloys based on IIA metals and the development of advanced getter materials for gas and vacuum technologies. This publication attempts to answer the current challenges in the field of gas sorption associated with the emergence of new vacuum products such as vacuum insulated glasses, electronic systems, cryogenic devices, etc. An analysis of the problems that arise here, as well as the results of sorption measurements, carried out with the participation of intermetallic phases of the composition CaLi2 and Ca0.33Li0.48Mg0.19, show that the best getter support for these new hermetically sealed products can be provided by intermetallic compounds formed in systems Li-IIA metals. Intermetallic phases of this family are easy to manufacture and demonstrate outstanding service characteristics: their specific sorption capacity is recorded high, exceeding traditional gas sorbents in this respect by at least an order of magnitude;the kinetics of gas capturing is set at the stage of alloy production, i.e., is adjustable;the temporary resistance of these phases to atmospheric gases allows to install the getter at its workplace in air, without further thermal activation. The sorption superiority of reactive intermetallics is explained by their special sorption mechanism: the gas/metal interaction is formed here as a combination of two processes, continuous growth of reaction products on a metallic surface and corrosion decay of brittle intermetallic phase under mechanical forces, which feeds the chemical reaction with a fresh surface. The advantages of sorption processes of this new type are undoubted and significant: compared with the conventional sorbents, an intermetallic getter reactant solves two important problems;it reduces production costs and increases the sorption yield.

Gaseous sorption and electrochemical properties of rare-earth hydrogen storage alloys and their representative applications： A review of recent progress

The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been systematically studied in order to improve storage capacity, kinetics, thermodynamics and electrochemical performance. In this review, we focus on recent research progress of gaseous sorption and electrochemical hydrogen storage properties of rare-earth alloys and highlight their commercial applications including hydrogen storage tanks and nickel metal hydride batteries. Furthermore, development trend and prospective of rare-earth hydrogen storage materials are discussed.

A Hierarchically Porous Metal-Organic Framework from Semirigid Ligand for Gas Adsorption

Hierarchically porous materials play an important role in facilitating mass transport and improving efficiency of adsorption and separation processes. In this paper, a new strategy is proposed to realize a hierarchically porous metal-organic framework （[Cu2（OH）（L）]＇（DMF）0.8 （FJU-11, H3L=3,5-（4-carboxybenzyloxy）benzoic acid, DMF= N,N-dimethylformamide） via using semi-rigid multi-carboxylic acids. Interestingly, FJU-11 possesses the large adsorption capacities and small isosteric heats toward CO2. The column breakthrough experiment for FJU-11 highlights its potential application in the separation of the flue gas.

The pore-fracture system properties of coalbed methane reservoirs in the Panguan Syncline,Guizhou,China

The Panguan Syncline contains abundant coal resources, which may be a potential source of coalbed methane. In order to evaluate the coalbed methane production potential in this area, we investi- gated the pore-fracture system of coalbed methane reservoirs, and analyzed the gas sorption and seepage capacities by using various analytical methods, including scanning electron microscopy （SEM）, optical microscopy, mercury-injection test, low-temperature N2 isotherm adsorption/desorption analyses, low- field nuclear magnetic resonance and methane isothermal adsorption measurements. The results show that the samples of the coal reservoirs in the Panguan Syncline have moderate gas sorption capacity. However, the coals in the study area have favorable seepage capacities, and are conductive for the coalbed methane production. The physical properties of the coalbed methane reservoirs in the Panguan Syncline are gener- ally controlled by coal metamorphism： the low rank coal usually has low methane sorption capacity and its pore and microfractures are poorly developed; while the medium rank coal has better methane sorption capacity, and its seepage pores and microfractures are well developed, which are sufficient for the coalbed methane＇s gathering and exploration. Therefore, the medium rank coals in the Panguan Syncline are the most prospective targets for the coalbed methane exploration and production.

Enhancement of gas-framework interaction in a metal–organic framework by cavity modification

Originated from the pore space segmentation modification of a reported metal-organic framework （MOF） （NOTT-125）, a new porous MOF ZnX was obtained and characterized by single-crystal X-ray diffraction, elemental analysis, X-ray powder diffraction and TGA. The ZnX exhibits remarkable selective CO2 adsorption property compared with that of the NOTT-125, which should be attributed to the enhanced gas-framework interactions induced by the fragmented pore space in ZnX.

Porous solid inspired hyper-crosslinked polymer liquids with highly efficient regeneration for gas purification

Separation media that combine the desired material properties within a single material for a given process remain an ongoing challenge for the gas separations in industry.Process integration of porous solid adsorbents is difficult due to their limited volumetric capacity,whereas issues of volatility and high regeneration temperatures exist for liquid amines and physical solvents.Herein,we report a family of polymer liquids inspired by hyper-crosslinked polymers(HCPs),a class of highly swellable network polymers.Compared with a chemically similar porous solid,the HCP-liquids demonstrate good volumetric capacity and improved selectivity of carbon dioxide over methane.Uptake appears to be enhanced by intramolecular swelling of the HCP-liquids at elevated pressures,while guests are strongly rejected from the HCP-liquids at slightly elevated temperatures,leading to highly efficient regeneration.Heat of adsorption and specific heat capacity of the HCP-liquids are also low,further suggesting favourable process thermodynamics.Additionally being easily prepared at scale,the presented HCP-liquids represent a promising step towards a material with the requisite properties to replace conventional scrubbing solvents to drastically reduce the footprint and energy needs of gas separations.

Frustrated Lewis pairs in situ formation in B-based porous aromatic frameworks for efficient o-phenylenediamine cyclization

Benzimidazoles are very important chemical materials in the pharmaceutical industry,and the most common synthetic route is cyclization of o-phenylenediamine with carbon sources,in which utilization of inexpensive and abundant CO_(2)as C1 source is very impressive.Porous aromatic frameworks(PAFs)with highly desired skeletons have attracted great attentions in gas capture and catalysis.Herein,B-based PAF-165 and PAF-166 are designed and synthesized via Friedel-Crafts alkylation reaction,which present high surface areas as well as high stability.Benefiting from the abundant electron-deficient B centers,both PAFs exhibit excellent selective CO_(2)adsorption abilities.The presence of sterically hindered B units in PAFs can act as Lewis acid active sites for the frustrated Lewis pairs(FLPs)in situ formation with ophenylenediamine,thus promoting the synthesis of benzimidazole.The optimal reaction conditions for o-phenylenediamine cyclization with PAF catalysts are explored,and the reaction mechanism is also proposed.This work provides feasible ideas for incorporating FLPs within porous materials as reusable heterogeneous catalysts for CO_(2)capture and conversion.

Dynamic properties of a flexible metal-organic framework exhibiting a unique"picture frame"-like crystal morphology

The precise control of the crystal morphology of metal-organic frameworks(MOFs)enables optimization of its adsorptive properties,as well as enables better integration within functional devices.However,the influence of such modifications on the dynamic properties of flexible MOFs is poorly understood Here,we report the synthesis of a series of Cu_(2)(bdc)_(2)(bpy)(bdc^(2-)=1,4-benzenedicarboxylate;bpy=4,4,-bipyridine)crystals having an unusual picture frame-like morphology that results from a restriction in the quantity of bpy pillars added to the reaction mixture during the intercalation of the Cu_(2)(bdc)_(2)(MeOH)_(2)layers.The width of the frames is found to correlate with the quantity of bpy,and importantly,causes the dynamic properties of the resulting Cu_(2)(bdc)_(2)(bpy)material to vary between rigid,elastic,and shape memory modes.In all,the results demonstrate the potential for the properties of MOFs to be optimized via subtle manipulations in the crystal morphology rather than changes in the overall material composition.

Truxene-based Conjugated Microporous Polymers via Different Synthetic Methods

Four truxene-based conjugated microporous polymers(Tr-CMPs)were prepared via different synthetic methods and their structure-property relationships were studied.The polymer networks have high Brunauer-Emmett-Teller(BET)specific surface areas ranging from 554 m^2·g^–1to 1024 m^2·g^–1.Pore sizes of the CMPs with different linkers are mainly located between 0.60 and 1.96 nm.Among all the Tr-CMPs,TrCMP4 has the highest BET surface area of 1024 m^2·g^–1and exhibits the highest H2 uptake of 0.88 wt%.Tr-CMP2 prepared by Suzuki-Miyaura coupling reaction has the highest photoluminescence quantum yields(PLQYs)of 13.06% and CO2 uptake of 6.25 wt%.

Underlying solvent-based factors that influence permanent porosity in porous liquids

Porous liquids(PLs)offer the potential to combine the ready handling and mature industry status of liquid absorbents,with the high permanent porosity of metal organic frameworks.To be functional,these nanocomposites need to satisfy a number of performance parameters,such as stability and viscosity of the porogen-solvent combination,avoiding solvent penetration into metal organic framework(MOF)pores,suitable capacities,and kinetics for gas sorption.In this work,we systematically investigate the component materials to elucidate the parametric space where stable photoluminescence(PL)can be generated.In this situation,deeper conclusions were able to be drawn with regard to the influence of hydrophobicity/philicity on the properties of the resulting nanocomposites.Zeolitic imidazolate frameworks(ZIFs)were combined with a range of solvents varying in steric bulk,to deliver CO_(2)sorption capacities as high as 4.2 mmol·g^(-1)at 10 bar.These findings may have broader implications for future investigations of this tantalising field of nanocomposites.

Synthesis of porous aromatic framework with Friedel–Crafts alkylation reaction for CO_2 separation

A novel porous aromatic framework, PAF-8, derived from tetraphenylsilane as basic building unit, was successfully synthesized via Friedel-Crafts alkylation reaction. This PAF material had high thermal stability as well as high surface area （785 m^2 g^-1） calculated from the Brunauer-Emmett-Teller （BET） model. Meanwhile, PAF-8 possessed high performances in gas sorption and especially for CO2 separation.