MOF-801 based solid phase microextraction fiber for the monitoring of indoor BTEX pollution.

Benzene, toluene, ethylbenzene and xylenes (BTEX) are some of the better-known indoor air pollutants, for which effective monitoring is important. The analysis of BTEX can be performed by different type of solid phase microextraction (SPME) fibers. This study presents a proposal for a low cost, convenient and environmentally friendly analytical method for the determination of BTEX in air samples using custom made SPME fibers. In this context, custom made metal organic frameworks (MOF-801) were coated on a stainless-steel wire for SPME fiber preparation. The analysis of BTEX was performed by introducing SPME fiber into an analyte-containing Tedlar bag in steady-state conditions. After the sampling step, the analytes were analyzed using gas chromatography mass spectrometry in selected ion monitoring mode. Parameters that affect the analysis results were optimized; these include desorption temperature and time, preconditioning time, extraction temperature and time, and sample volume. Under optimized conditions, analytical figure of merits of developed method were obtained, including limits of detection (LOD) (0.012 - 0.048 mg/m3), linear ranges (0.041-18 mg/m3), intraday and interday repeatability (2.08 - 4.04% and 3.94 - 6.35%), and fiber to fiber reproducibility (7.51 - 11.17%). The proposed method was successfully applied to real air samples with an acceptable recovery values between 84.5% and 110.9%. The developed method can be applied for the effective monitoring of BTEX.

Sensitivity to NH3 Vapor: Synthesis and Characterization of Five New Coordination Polymers Based on 2,2-Dimethylglutaric Acid and Bis(triazole)-Derived Ligands.

Five new coordination polymers (CPs) were obtained as a result of hydrothermal reactions of 2,2-dimethylglutaric acid (H2dmg) and 1,4-bis(1H-1,2,4-triazol-1-ylmethyl)benzene (pbtx)/1,2-bis(1H-1,2,4-triazol-1-ylmethyl)benzene (obtx) ligands with some metal ions [Co(µ-dmg)(µ-obtx)]n (1), [Zn(µ-dmg)(µ-obtx)]n (2), [Cd(µ-dmg)(µ-obtx)]n (3), [Co2(µ-dmg)2(µ-pbtx)2]n (4), and [Cd(µ-dmg)(H2O)(µ-pbtx)]n (5). All of the compounds were characterized by elemental analysis, FT-IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analysis techniques. The single-crystal X-ray studies show that all compounds exhibit 2D layer structures. To examine the ammonia sensing properties of five new coordination complexes (1-5), the absorption and emission spectra of CPs embedded in ethyl cellulose thin films were measured by exposure to different concentrations of ammonia (NH3) vapor. The [Co2(µ-dmg)2(µ-pbtx)2]n (4)-based sensor agent was found to show promising sensor properties in detecting NH3 vapor.

Oxalamide-Functionalized Metal Organic Frameworks for CO2 Adsorption.

Metal-organic frameworks (MOFs) have received great attention in recent years as potential adsorbents for CO2 capture due to their unique properties. However, the high cost and their tedious synthesis procedures impede their industrial application. A series of new CO2-philic oxalamide-functionalized MOFs have been solvothermally synthesized: {[Zn3(µ8-OATA)1.5(H2O)2(DMF)]·5/2H2O·5DMF}n (Zn-OATA), {[NH2(CH3)2][Cd(µ4-HOATA)]·H2O·DMF}n (Cd-OATA), and {[Co2(µ7-OATA)(H2O)(DMF)2]·2H2O·3DMF}n (Co-OATA) (H4OATA = N,N'-bis(3,5-dicarboxyphenyl)oxalamide). In Zn-OATA, the [Zn2(CO2)4] SBUs are connected by OATA4- ligands into a 3D framework with 4-connected NbO topology. In Cd-OATA, two anionic frameworks with a dia topology interpenetrated each other to form a porous structure. In Co-OATA, [Co2(CO2)4] units are linked by four OATA4- to form a 3D framework with binodal 4,4-connected 42·84 PtS-type topology. Very interestingly, Cu-OATA can be prepared from Zn-OATA by a facile metal ions exchange procedure without damaging the structure while the CO2 adsorption ability can be largely enhanced when Zn(II) metal ions are exchanged to Cu(II). These new MOFs possess channels decorated by the CO2-philic oxalamide groups and accessible open metal sites, suitable for highly selective CO2 adsorption. Cu-OATA exhibits a significant CO2 adsorption capacity of 25.35 wt % (138.85 cm3/g) at 273 K and 9.84 wt % (50.08 cm3/g) at 298 K under 1 bar with isosteric heat of adsorption (Qst) of about 25 kJ/mol. Cu-OATA presents a very high selectivity of 5.5 for CO2/CH4 and 43.8 for CO2/N2 separation at 0.1 bar, 298 K. Cd-OATA exhibits a CO2 sorption isotherm with hysteresis that can be originated from structural rearrangements. Cd-OATA adsorbs CO2 up to 11.90 wt % (60.58 cm3/g) at 273 K and 2.26 wt % (11.40 cm3/g) at 298 K under 1 bar. Moreover, these new MOFs exhibit high stability in various organic solvents, water, and acidic or basic media. The present work opens a new opportunity in the development of improved and cost-effective MOF adsorbents for highly efficient CO2 capture.

Tris(ethyl-enediamine)-nickel(II) 1H-pyrazole-3,5-dicarboxyl-ate 1.67-hydrate.

The asymmetric unit of the title compound, [Ni(C(2)H(8)N(2))(3)](C(5)H(2)N(2)O(4))·1.67H(2)O, consists of three [Ni(en)(3)](2+) dications (en is ethyl-enediamine), three [(pzdc)(3)](2-) dianions (pzdc is pyrazole-3,5-dicarboxyl-ate) and five water mol-ecules. In each complex dication, the Ni(II) atom is coordinated by six N atoms from three en ligands forming a distorted octa-hedral coordination geometry. In the crystal, the ions and water mol-ecules are linked into a three-dimensional framework by a large number of N-H⋯O and O-H⋯O hydrogen bonds.

Diaqua-bis(1,3-propane-diamine)nickel(II) squarate tetrahydrate.

The asymmetric unit of the title compound, [Ni(C(3)H(10)N(2))(2)(H(2)O)(2)](C(4)O(4))·4H(2)O, contains one-half of the diaqua-bis(1,3-propane-diamine)nickel(II) cation, one-half of the centrosymmetric squarate anion and two uncoordinated water mol-ecules. In the cation, the Ni(II) atom is located on a crystallographic inversion centre and has a slightly distorted octa-hedral coordination geometry. The six-membered chelate ring adopts a chair conformation. O-H⋯O hydrogen bonds link the cation and anion through the water mol-ecule, while N-H⋯O hydrogen bonds link the cation and anion and cation and water mol-ecules. In the crystal structure, inter-molecular O-H⋯O and N-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network structure.