Refine
Document Type
- Article (reviewed) (14)
Has Fulltext
- no (14)
Is part of the Bibliography
- yes (14)
Keywords
- Adsorption (4)
- Metallorganisches Netzwerk (4)
- Kohlenstoff (3)
- Molekularsieb (2)
- Nanotechnologie (2)
- Sorption (2)
- Differenz (1)
- Flexibilität (1)
- Funktionalität (1)
- Gas (1)
- Gasbehälter (1)
- Gasgemisch (1)
- Isoglosse (1)
- Kinetik (1)
- Kupfer (1)
- Leitfähige Polymere (1)
- Luftzerlegung (1)
- Methan (1)
- Nanopartikel (1)
- Netzwerk (1)
- Oberflächenbehandlung (1)
- Phosphate (1)
- Polyethylene (1)
- Porosität (1)
- Rauchgas (1)
- Raumgitter (1)
- Schaufelrad (1)
- Simulation (1)
- Wasserstoffspeicherung (1)
- Werkstoff (1)
- organische Verbindung (1)
Institute
Open Access
- Closed Access (10)
Selective separation of CO2-CH4 mixed gases via magnesium aminoethylphosphonate nanoparticles
(2016)
Pure gas adsorption isotherms of CH4 and N2 and their binary mixtures were measured at 273 K, 298 K and 323 K and up to 2 MPa on two different microporous metal–organic frameworks (MOFs), i.e. the commercially available Basolite® A100 and the recently reported copper-based triazolyl benzoate MOF 3∞[Cu(Me-4py-trz-ia)] (1). The Tòth isotherm model and the vacancy solution model were used to describe the experimentally determined isotherms and proved to be well suited for this purpose. While 1 shows a more homogeneous surface with a nearly constant isosteric heat of adsorption of 18–18.5 kJ mol−1 for CH4 and 12–15 kJ mol−1 for N2, the isosteric heat of adsorption at zero coverage for Basolite® A100 is 19 kJ mol−1 for CH4 and 16.2 kJ mol−1 for N2, decreasing significantly with increasing loading. Binary adsorption isotherms were measured gravimetrically to determine the total adsorbed mass of CH4 and N2. The van Ness method was successfully applied to calculate partial loadings from gravimetrically measured binary adsorption isotherms. Further studies by volumetric–chromatographic experiments support the good correlation between experimental data and predictions by the vacancy solution model (VSM-Wilson) and the ideal adsorbed solution theory (IAST) from pure gas isotherms. The experimental selectivities were determined to be αCH4/N2 = 4.0–5.0 for 1, slightly higher than for Basolite® A100 with αCH4/N2 = 3.4–4.5. These values are in good agreement with predictions for ideal selectivities based on Henry's law constants. From the experimental selectivities the potential of both MOFs in gas separation of CH4 from N2 can be derived.
We tested the MOF framework Cu-BTC for natural gas (NG) storage. Adsorption isotherms of C1–C4 alkanes were simulated applying the Grand Canonical ensemble and the Monte Carlo algorithm in a classical molecular mechanics approach. Experimental monocomponent isotherm of the alkanes was used to validate the force field. We performed multicomponent adsorptions calculations for three different quaternary mixtures of C1–C4 alkanes, matching typical NG streams composition, and predicted theoretical storage capacities, efficiency and accumulation of the NG within that composition. Despite being one of the frameworks with greatest storage capacity of methane, we found that Cu-BTC presented great sensitivity to the variation of the heavier alkanes in NG composition. When we increase the percentage of butane from 0.1% to 0.7% in the mixture, the mass of components retained in the discharge pressure (1 bar) increases from 35 to 60%. We also perform siting and interaction energy investigations and compare the NG storage performance of the Cu-BTC with that of activated carbons. To our knowledge, this is the first study regarding the efficiency of the NG storage in Cu-BTC.
An isomorphous series of 10 microporous copper-based metal–organic frameworks (MOFs) with the general formulas ∞3[{Cu3(μ3-OH)(X)}4{Cu2(H2O)2}3(H-R-trz-ia)12] (R = H, CH3, Ph; X2– = SO42–, SeO42–, 2 NO32– (1–8)) and ∞3[{Cu3(μ3-OH)(X)}8{Cu2(H2O)2}6(H-3py-trz-ia)24Cu6]X3 (R = 3py; X2– = SO42–, SeO42– (9, 10)) is presented together with the closely related compounds ∞3[Cu6(μ4-O)(μ3-OH)2(H-Metrz-ia)4][Cu(H2O)6](NO3)2·10H2O (11) and ∞3[Cu2(H-3py-trz-ia)2(H2O)3] (12Cu), which are obtained under similar reaction conditions. The porosity of the series of cubic MOFs with twf-d topology reaches up to 66%. While the diameters of the spherical pores remain unaffected, adsorption measurements show that the pore volume can be fine-tuned by the substituents of the triazolyl isophthalate ligand and choice of the respective copper salt, that is, copper sulfate, selenate, or nitrate.
Pure component sorption isotherms of n-butane, isobutane, 1-butene and isobutene on the metal–organic framework (MOF) 3∞[Cu4(μ4-O)(μ2-OH)2(Me2trz-pba)4] at various temperatures between 283 K and 343 K and pressures up to 300 kPa are presented. The isotherms show a stepwise pore filling which is typical for structurally flexible materials with broad adsorption–desorption hysteresis loops. Gate opening pressures in their endemic characteristic depend on the used hydrocarbon gases. From all investigated gases only the isotherms of 1-butene present a second step at a relative pressure above p/p0 = 0.55. As a consequence, only 1-butene can fully open the framework resulting in a pore volume of 0.54 cm3 g−1. This result is in good agreement with the value of 0.59 cm3 g−1 calculated based on single crystal structure data. The isosteric heat of adsorption was calculated from the experimental isotherms for all C4-isomers. At low loadings the isosteric heat is in a narrow region between 41 and 49 kJ mol−1. Moreover, in situ XRD measurements at different relative hydrocarbon pressures were performed at 298 K for the C4-isomers. The differences in the pressure-depending powder diffraction patterns indicate phase transitions as a result of adsorption. Similar diffraction patterns were observed for all C4-hydrocarbons, except 1-butene, where the second step at higher relative pressure (p/p0 > 0.55) is accompanied by an additional phase transition. This powder pattern resembles that of the as-synthesized MOF material containing solvent molecules in the pore system. The resulting structural changes of the material during guest and pressure induced external stimuli are evidenced by the new coupled XRD adsorption equipment.
Two closely related series of paddle-wheel-based triazolyl isophthalate MOFs are presented. Thermal and CO2 adsorption studies reveal network flexibility induced by alkyl substituents of the linker. By choice of the substituent, the pore volumes and pore diameters can be adjusted. Fine-tuning of the gate opening pressure and the hysteresis shape is possible by modulating the substitution pattern and by choice of the metal ion.
Phosphate-based inorganic–organic hybrid nanoparticles (IOH-NPs) with the general composition [M]2+[Rfunction(O)PO3]2– (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3]2– is a fluorescent dye anion ([RdyeOPO3]2–), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO]2+[PUP]2–, [ZrO]2+[MFP]2–, [ZrO]2+[RRP]2–, and [ZrO]2+[DUT]2– (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3]2–), drug transport and release of anti-inflammatory ([ZrO]2+[BMP]2–) and antitumor agents ([ZrO]2+[FdUMP]2–) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5′-fluoro-2′-deoxyuridine 5′-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO]2+[BMP]2–0.996[DUT]2–0.004. Merging of functional anions, in general, results in [ZrO]2+([RdrugOPO3]1–x[RdyeOPO3]x)2– nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO]2+[RaminePO3]2– IOH-NPs, finally, show CO2 sorption (up to 180 mg g–1) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP]2–, 1-aminoethyl phosphonate [1AEP]2–, 2-aminoethyl phosphonate [2AEP]2–, aminopropyl phosphonate [APP]2–, and aminobutyl phosphonate [ABP]2–. All [M]2+[Rfunction(O)PO3]2– IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.