With the development of better catalysts, mass transport limitations are becoming a challenge to high throughput electrochemical reduction of CO 2 to CO. In contrast to optimization of electrodes for fuel cells, optimization of gas diffusion electrodes (GDE)consisting of a carbon fiber substrate (CFS), a micro porous layer (MPL), and a catalyst layer (CL)for CO 2 reduction has not received a lot of attention. Here, we studied the effect of the MPL and CFS composition on cathode performance in electroreduction of CO 2 to CO. In a flow reactor, optimized GDEs exhibited a higher partial current density for CO production than Sigracet 35BC, a commercially available GDE. By performing electrochemical impedance spectroscopy in a CO 2 flow reactor we determined that a loading of 20 wt% PTFE in the MPL resulted in the best performance. We also investigated the influence of the thickness and wet proof level of CFS with two different feeds, 100% CO 2 and the mixture of 50% CO 2 and N 2 , determining that thinner and lower wet proofing of the CFS yields better cathode performance than when using a thicker and higher wet proof level of CFS.

Herein we report a new microwave-assisted synthetic strategy to rapidly prepare hybrid zeolitic–imidazolate frameworks (ZIFs): ZIFs with mixed metal centers and/or mixed linkers.

The relatively slow and complex fabrication processes of polycrystalline metal-organic framework (MOF) membranes often times restrict their way to commercialization, despite their potential for molecular separation applications. Herein, we report a rapid one-pot microwave synthesis of mixed-linker hybrid zeolitic-imidazolate framework (ZIF) membranes consisting of 2-methylimidazolate (ZIF-8 linker) and benzimidazolate (ZIF-7 linker) linkers, termed ZIF-7-8 membranes. The fast-volumetric microwave heating in conjunction with a unique counter diffusion of metal and linker solutions enabled unprecedented rapid synthesis of well-intergrown ZIF-7-8 membranes in ∼90 s, the fastest MOF membrane preparation up to date. Furthermore, we were able to tune the molecular sieving properties of the ZIF-7-8 membranes by varying the benzimidazole-to-2-methylimidazole (bIm-to-mIm) linker ratio in the hybrid frameworks. The tuning of their molecular sieving properties led to the systematic change in the permeance and selectivity of various small gases. The unprecedented rapid synthesis of well-intergrown ZIF-7-8 membranes with tunable molecular sieving properties is an important step forward for the commercial gas separation applications of ZIF membranes.

Pulsed field gradient (PFG) NMR was used in combination with single crystal IR microscopy (IRM) to study diffusion of ethane inside crystals of a mixed linker zeolitic imidazolate framework (ZIF) of the type ZIF-7-8 under comparable experimental conditions. These crystals contain 2-methylimidazolate (ZIF-8 linker) and benzimidazolate (ZIF-7 linker). It was observed that the PFG NMR attenuation curves measured for ethane in ZIF-7-8 exhibit deviations from the monoexponential behaviour, thereby indicating that the ethane self-diffusivity in different crystals of a crystal bed can be different. Measurements of the ethane uptake curves performed by IRM under the same conditions in different ZIF-7-8 crystals of the bed yield different transport diffusivities thus confirming that the rate of ethane diffusion is different in different ZIF-7-8 crystals. The IRM observation that the fractions of ZIF-8 and ZIF-7 linkers are different in different ZIF-7-8 crystals allowed attributing the observed heterogeneity in diffusivities to the heterogeneity in the linker fraction. The quantitative comparison of the average ethane self-diffusivities measured by PFG NMR in ZIF-7-8 with the corresponding data on corrected diffusivities from IRM measurements revealed a good agreement between the results obtained by the two techniques. In agreement with the expectation of smaller aperture sizes in ZIF-7-8 than in ZIF-8, the average ethane self-diffusivities in ZIF-7-8 were found to be significantly lower than the corresponding self-diffusivities in ZIF-8.

Zeolitic imidazolate frameworks (ZIFs) have gained much interest due to their potentials in gas separations. A hybrid approach by mixing metals and/or linkers has been recently investigated to fine-tune the ZIF framework porosity and surface properties and potentially extending their separation applications for many important gas mixtures. In general, the hybrid approach requires mixing of isostructural ZIFs to maintain their topology, thus limiting the options of linkers and metal centers to obtain hybrid ZIFs. Linkerdoping, as reported here, can be a strategy to expand the option of imidazolate linkers to obtain mixed-linker hybrid ZIFs. Two linkers are investigated to be doped into the ZIF-8 framework: 2-ethylimidazole (eIm) and 2-phenylimidazole (phIm). The linker-doping strategy is shown to tune the "stiffness" of Zn−N bonding as characterized by FT-IR, thereby the linker flip-flopping motion of ZIF-8, which is analyzed through gas adsorption isotherms. Furthermore, well-intergrown ultrathin eIm-doped ZIF-8 membranes are grown on α-Al 2 O 3 substrates, in which the incorporation of eIm affects the morphology and thickness of the polycrystalline membranes, improving the permeance of propylene and propane molecules.

We present anovel synthesis strategy termed delayed linker addition (DLA) to synthesize hybrid zeolitic-imidazolate frameworks containing unsubstituted imidazolate linkers (Im) with SOD topology (hereafter termed Im/ZIF-8). Im linker incorporation can create larger voids and apertures, which are important properties for gas storage and separation. To date,there have been only ahandful of reports of Im linkers incorporated into ZIF-8 frameworks,t ypically requiring arduous and complicated post synthesis approaches.D LA, as reported here,i sasimple one-step synthesis strategy allowing high incorporation of Im linker into the ZIF-8 framework while still retaining its SOD topology.W ef abricated mixedmatrix membranes (MMMs) with 6FDA-DAM polymer and Im/ZIF-8 obtained via DLA as af iller.T he Im/ZIF-8containing MMMs showed excellent performance for both propylene/propane and n-butane/i-butane separation, displaying permeability and ideal selectivity well abovet he polymer upper bound. Moreover,highly detailed molecular simulations shed light to the aperture sizea nd flexibility response of Im/ ZIF-8 and its improved diffusivity as compared to ZIF-8.

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