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91.
Strategies for hydrogen storage in metal--organic frameworks 总被引:11,自引:0,他引:11
Increased attention is being focused on metal-organic frameworks as candidates for hydrogen storage materials. This is a result of their many favorable attributes, such as high porosity, reproducible and facile syntheses, amenability to scale-up, and chemical modification for targeting desired properties. A discussion of several strategies aimed at improving hydrogen uptake in these materials is presented. These strategies include the optimization of pore size and adsorption energy by linker modification, impregnation, catenation, and the inclusion of open metal sites and lighter metals. 相似文献
92.
Angelika Basch Silvia Gross Namita Roy Choudhury Janis Matisons 《Journal of Sol-Gel Science and Technology》2005,33(1):39-45
New inorganic-organic hybrid materials were prepared by free-radical polymerization of methyl methacrylate (MMA) with methacrylate-substituted oxotantalum cluster [Ta4O4(OEt)8(OMc)4] and their properties evaluated. The cluster was prepared by the reaction of the parent alkoxide with methacrylic acid. Samples of the hybrid materials were produced with Ta-cluster to methyl methacrylate in the ratios of 1:50 and 1:100 and were characterized by thermal and spectroscopic techniques. The glass transition temperatures of the hybrid materials are shifted to higher temperatures than pure PMMA as a result of cross-linking of the polymer by the oxotantalum clusters. The increase in Tg is also observed from the dynamic mechanical analysis (DMA). Evidence of crosslinking between the Ta-cluster and PMMA is obtained from infrared spectroscopic study. Surface studies performed by X-ray photoelectron spectroscopy (XPS) provide information about the atomic concentrations of the surface and indicate tantalum bonded to oxygen. 相似文献
93.
Vítězslav Zima Jan Svoboda Klára Melánová Ji?í Dybal 《Journal of solid state chemistry》2007,180(3):929-939
Several new strontium 4-carboxyphenylphosphonates, i.e., two modifications of Sr(HOOCC6H4PO3H)2, SrH(OOCC6H4PO3)·H2O, Sr3(OOCC6H4PO3)2·4H2O and Sr3(OOCC6H4PO3)2·5.7H2O were prepared and characterized by elemental analysis, thermogravimetry, X-ray powder diffraction and infrared spectroscopy. It was found that the compositions of these compounds depend on the acidity of the reaction medium. In addition, the presented compounds are interconvertible in dependence on pH. The position of the acid hydrogen atom in SrH(OOCC6H4PO3)·H2O was determined from the IR spectra of the studied compounds.The structure of the β modification of Sr(HOOCC6H4PO3H)2 was solved from its X-ray powder diffraction pattern using an ab initio method (the FOX program) with subsequent Rietveld refinement in the FULLPROF program. The compound is monoclinic, with the space group P21/c (No. 14), a=49.88(2), b=7.867(2), c=5.602(3) Å, β=128.68(2)°, and Z=4. It has a one-dimensional structure with an inorganic part built of SrO8 distorted tetragonal antiprisms. 相似文献
94.
Alufelwi M. Tshavhungwe Marcus Layh Neil J. Coville 《Journal of Sol-Gel Science and Technology》2004,29(3):167-177
Bifunctional periodic mesoporous organosilica materials with and without cobalt ion incorporation were synthesized by co-condensation of 1,2-bistrimethoxysilylethane (BTME) with 3-glycidoxypropyltriethoxysilane (GPTS) in the presence of cetyltrimethylammonium bromide. Nitrogen gas adsorption on samples with varying ratios of BTME:GPTS revealed that increasing the amount of GPTS affects pore size, surface area and pore volume as well as shapes of the isotherms and hysteresis loops. The hysteresis loops of the Type IV isotherms obtained for GPTS-modified ethane silica materials (without cobalt ion) change from Type H3 to Type H4 with increasing GPTS content. There is a tendency for pore sizes to change from mesopore to micropore when the amount of GPTS is increased. Isotherms of cobalt ion incorporated GPTS-modified ethane silica materials change from Type IV to Type I with increasing GPTS content. The surface area, pore volume and pore diameter decrease with increasing loading of GPTS as well as after cobalt ion incorporation. Thermogravimetric analysis and differential thermal analysis show that the surfactant is removed by solvent extraction. Cobalt ion incorporation is confirmed by powder X-ray diffraction and Raman spectroscopy. 相似文献
95.
Chemical Modification of Silica Gels 总被引:2,自引:0,他引:2
Highly porous pure and polyethyleneglycol (PEG)-doped silica gels have been prepared from tetraethyl orthosilicate (TEOS) in ethanol using NH4OH base-catalysis. Addition of PEG to the SiO2-system increases the average particle size and most frequent pore diameter of the resultant gels while their total surface area decreases. The viscosity of the sol increases with PEG concentration and passes through a maximum with increasing molecular weight at PEG 200. Results obtained indicate a definite interaction of the polymer with SiO2 and that this interaction is not as a result of direct formation of Si– O– C linkage, but is more likely to be due to hydrogen bonding between the hydrated PEG and the Si– O– Si network. Structure-process correlations are considered. 相似文献
96.
97.
Toshiharu Okui Yuriko Saito Tatsuya Okubo Masayoshi Sadakata 《Journal of Sol-Gel Science and Technology》1995,5(2):127-134
Selective gas permeation of porous organic/inorganic hybrid membranes via sol-gel route and its thermal stability are described. Separation performance of the hybrid membrane was improved compared with porous membranes governed by the Knudsen flow, and gas permeability was still much higher than that through nonporous membranes. Additionally, it was shown that these membranes were applicable at higher temperatures than organic membranes.SEM observation demonstrated that the thin membrane was crack-free. Nitrogen physisorption isotherms showed the pore size was in the range of nanometers. Gas permeability through this membrane including phenyl group was in the range of 10–8 [cc(STP) cm/(cm2 s cmHg)] at 25°C. The ratios of O2/N2 and CO2/N2 were 1.5 and 6.0, respectively, showing the permeation was not governed by the Knudsen flow. The permeability decreased as the temperature increased. Furthermore, the specific affinity between gas molecules and surface was observed not only in the permeation data of the hybrid membranes but in the physisorption data. These results suggested that the gas permeation through the hybrid membrane was governed by the surface flow mechanism.Thermal analysis indicated that these functional groups were still stable at higher temperatures. The phenyl group especially remained undamaged even at 400°C. 相似文献
98.
在浓盐酸水溶液中,碘化N,N-二甲基-1,5-二氮杂环[3.2.1]辛烷([3.2.1-Me2dabco]I2)和碘化1-氨基-1,4-二氮杂环[2.2.2]辛烷([2.2.2-NH2dabco]I)与氯化铜反应得到2种有机-无机杂化铜化合物[3.2.1-Me2dabco][CuCl4](1)和[2.2.2-NH2dabco][CuCl4](2)。X射线单晶结构衍射证实化合物1和2中的无机阴离子是[CuCl4]2-四面体。化合物1和2表现出可逆的热致变色现象,随着温度升高,它们的颜色从黄色变为红色,这应该是由[CuCl4]2-四面体的变形引起的。 相似文献
99.
Daniel Ayuk Mbi Egbe Eckhard Birckner Elisabeth Klemm 《Journal of polymer science. Part A, Polymer chemistry》2002,40(15):2670-2679
Luminophoric dialdehyde 1,4‐bis[4‐formylphenylethynyl‐(2,5‐dioctadecyloxyphenyl)‐buta‐1,3‐diyne] ( 4 ) enables the synthesis of diyne‐containing hybrid polyphenyleneethynylene/poly(p‐phenylenevinylene) polymer poly[1,4‐phenylene‐ethynylene‐1,4‐(2,5‐dioctadecyloxy)phenylene‐butadi‐1,3‐ynylene‐1,4‐(2,5‐dioctadecyloxy)phenylene‐ethynylene‐1,4‐phenylene‐ethene‐1,2‐diyl‐1,4‐(2,5‐dioctadecyloxy)phenylene‐ethene‐1,2‐diyl] ( 7 ) with a well‐defined general structure (? Ph? C?C? Ar? C?C? C?C? Ar? C?C? Ph? CH?CH? Ar? CH?CH? )n, which was confirmed by NMR and infrared spectroscopy. The highly luminescent material is thermostable, soluble in usual organic solvents through the grafting of octadecyloxy side groups, and can be processed into transparent films. With the aim to investigate the effect of ? C?C? C?C? in the photophysical behavior of 7 , a comparison of the photophysics of monomers 3 [1,4‐bis(4‐formylphenylethynyl)‐2,5‐dioctadecyloxybenzene] and 4 and subsequently of their respective polymers 6 and 7 has been carried out. Similar photophysical behaviors for 6 (poly[1,4‐phenylenethynylene‐1,4‐(2,5‐dioctadecyloxyphenylene)ethene‐1,2‐diyl]) and 7 were observed in dilute CHCl3 solution as a result of an identical chromophore system responsible for the absorption (λa = 448 nm) and emission (λf = 490 nm) in both compounds. The increased planarization and enhanced rigidity of the conjugated backbone in the solid state at room temperature as well as in frozen dilute tetrahydrofuran solution at 77 K cause the bathochromic shift of the absorption and emission spectra. The large octadecyloxy side chains obviously limit strong π‐π interchain interactions in the solid films, which explains the high fluorescence quantum yields of 35 and 52% obtained for 6 and 7 , respectively. The energetically arduous migration of the π electron through the diyne units not only requires a higher threshold voltage for the detection of photoconductivity in 7 but could possibly limit radiationless deactivation channels of the exciton, which explains the approximate 20% fluorescence quantum yields difference between 6 and 7 in the solid state. The electron‐withdrawing effect of the triple bonds confer both 6 and 7 with a good electron‐accepting property (Eox = 1.39 V vs Ag/AgCl) if used in light‐emitting diode devices. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2670–2679, 2002 相似文献
100.
Fan J Gan L Kawaguchi H Sun WY Yu KB Tang WX 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3965-3973
Six noninterpenetrating organic-inorganic hybridized coordination complexes, [Mn(3)(2)(H(2)O)(2)](ClO(4))(2).2 H(2)O (5), [Mn(3)(2)(H(2)O)(2)](NO(3))(2) (6), [Mn(3)(2)(N(3))(2)].2 H(2)O (7), [Cu(3)(2)(H(2)O)(2)](ClO(4))(2) (8), [Mn(4)(2)(H(2)O)(SO(4))].CH(3)OH.5 H(2)O (9) and [Mn(4)(2)](ClO(4))(2) (10) were obtained through self-assembly of novel tripodal ligands, 1,3,5-tris(1-imidazolyl)benzene (3) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (4) with the corresponding metal salts, respectively. Their structures were determined by X-ray crystallography. The results of structural analysis of complexes 5, 6, 7, and 8 with rigid ligand 3 indicate that their structures are mainly dependant on the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and metal ions. While in complexes 9 and 10, which contain the flexible ligand 4, the counteranion plays an important role in the formation of the frameworks. Entirely different structures of complexes 5 and 10 indicate that the organic ligands greatly affect the structures of assemblies. Furthermore, in complexes 5 and 6, the counteranions located between the cationic layers can be exchanged by other anions. Reversible anion exchanges between complexes 5 and 6 without destruction of the frameworks demonstrate that 5 and 6 can act as cationic layered materials for anion exchange, as determined by IR spectroscopy, elemental analyses, and X-ray powder diffraction. 相似文献