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Zeolitic imidazolate frameworks (ZIFs) are hybrid organic-inorganic microporous materials that exhibit zeolite-like structures and can be synthesized with a wide range of pore sizes and chemical functionality. ZIFs as thin films and membranes are of interest for their applications in sensors and gas separation. Here, we report a method for ZIF film and membrane fabrication, based on support surface modification and in situ solvothermal growth, which has potential for general application to other ZIF membranes. Our simple surface modification method results in strong covalent bonds between α-Al(2)O(3) supports and imidazolate ligands, which promote the heterogeneous nucleation and growth of ZIF crystals. The microstructure of ZIF-8 films can be controlled by controlling the pH of the growth solution. ZIF-7 films were fabricated to demonstrate the potential for general applicability of our method. Finally, the separation performance of several ZIF-8 membranes was evaluated, revealing molecular sieving behavior with an ideal selectivity for H(2)/CH(4) of 13.

Metal–organic frameworks (MOFs) are hybrid organic–inorganic nanoporous materials that exhibit regular crystalline lattices with relatively well-defined pore structures. Chemical functionalization of the organic linkers in the structures of MOFs affords facile control over pore size and chemical/physical properties, making MOFs attractive for a variety of industrial applications including membrane-based gas separations. A wealth of reports exists discussing the synthesis and applications of MOFs; however, relatively few reports exist discussing MOF membranes. This disparity owes to challenges associated with fabricating films of MOF materials, including poor substrate–film interactions, moisture sensitivity, and thermal/mechanical instability. Since even nanometer-scale cracks and defects can affect the performance of a membrane for gas separation, these challenges are particularly acute for the fabrication of MOF membranes. Here, we review recent progress on MOF membranes with an emphasis on their fabrication techniques, challenges involved in membrane synthesis, reported strategies to address these challenges (issues), and gas separation performance. Finally, we conclude with our perspectives on future research directions in this area.

Supplemental information Given that air samples stored in metal have been known to sometimes have in-growth of H 2 when stored for significant periods of time, there was concern over the stability of H 2 in the canisters from the Whole Air Sampler. To investigate for this possibility, we analyzed five canister/flask sample pairs that had aliquots separated into evacuated glass flasks 14 to 15 months after initial sampling and ~ 6 months prior to isotopic analysis. Under these

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Metal-organic frameworks (MOFs) are attractive for gas separation membrane applications due to their microporous channels with tunable pore shape, size, and functionality. Conventional MOF membrane fabrication techniques, namely in situ and secondary growth, pose challenges for their wider commercial applications. These challenges include reproducility, scalability, and high manufacturing cost. Recognizing that the coordination chemistry of MOFs is fundamentally different from the covalent chemistry of zeolites, we developed a radically different strategy for MOF membrane synthesis. Using this new technique, we were able to produce continuous well-intergrown membranes of prototypical MOFs, HKUST-1 and ZIF-8, in a relatively short period of time (tens of min). With a minimal consumption of precursors and a greatly simplified synthesis protocol, our new technique provides potential for a continuous, scalable, reproducible, and easily commercializable route for the rapid synthesis of MOF membranes. RTD-prepared MOF membranes show greatly improved gas separation performances as compared to those prepared by conventional solvothermal methods, indicating improved membrane microstructure.

Abstract. Emissions from oil and natural gas development during winter in the Upper Green River basin of Wyoming are known to drive episodic ozone (O3) production. Contrasting O3 distributions were observed in the winters of 2011 and 2012, with numerous episodes (hourly O3 ≥ 85 ppbv) in 2011 compared to none in 2012. The lack of O3 episodes in 2012 coincided with a reduction in measured ambient levels of total non-methane hydrocarbons (NMHC). Measurements of speciated NMHC, and other air quality parameters, were performed to better understand emission sources and to determine which compounds are most active in promoting O3 formation. Positive matrix factorization (PMF) analyses of the data were carried out to help achieve these goals. PMF analyses revealed three contributing factors that were identified with different emission source types: factor 1, combustion/traffic; factor 2, fugitive natural gas; and factor 3, fugitive condensate. Compositional signatures of the three contributing factors were identified through comparison with independently derived emission source profiles. Fugitive emissions of natural gas and of condensate were the two principal emission source types for NMHC. A water treatment and recycling facility was found to be a significant source of NMHC that are abundant in condensate, in particular toluene and m+p-xylene. Emissions from water treatment have an influence upon peak O3 mixing ratios at downwind measurement sites.

[1] New high-precision measurements of the carbon and hydrogen isotopic compositions of stratospheric CH 4 made on whole air samples collected aboard the NASA ER-2 aircraft are compared with results from the Lawrence Livermore National Laboratory 2-D model. Model runs incorporating sets of experimentally determined kinetic isotope effects (KIEs) for the reactions of CH 4 with each of the oxidants OH, O( 1 D), and Cl are examined with the goals of determining (1) how well the 2-D model can reproduce the observations for both the carbon and hydrogen isotopic compositions, (2) what factors are responsible for the observed increase in the apparent isotopic fractionation factors with decreasing methane mixing ratios, and (3) how sensitive the modeled isotopic compositions are to various experimentally determined KIEs. Bound by estimates of the effects of uncertainties in model chemistry and transport on isotopic compositions, we then examine the constraints the ER-2 observations place on values for the KIEs. For the carbon KIE for reaction of CH 4 with O( 1 D), for example, the analysis of model results and observations favors the larger of the experimental values, 1.013, over a value of 1.001. These analyses also suggest that intercomparisons of results from different models using a given set of KIEs may be useful as a new diagnostic of model-model differences in integrated chemistry and transport.