Composites incorporating two-dimensional nanostructures within polymeric matrices hold potential as functional components for several technologies, including gas separation. Prospectively, employing metal-organic-frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of free standing nanosheets has proven challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometer lateral dimensions and nanometer thickness. Incorporating MOF nanosheets into polymer matrices endows the resultant composites with outstanding CO2 separation performance from CO2/CH4 gas mixtures, together with an unusual and highly desired increment in the separation selectivity with pressure. As revealed by tomographic focused-ion-beam scanning-electron-microscopy, the unique separation behaviour stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared to isotropic crystals, which improves the efficiency of molecular discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications.

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The preparation and the performance of mixed matrix membranes based on metal-organic polyhedra (MOPs) are reported. MOP fillers can be dispersed as discrete molecular units (average 9 nm in diameter) when low filler cargos are used. In spite of the low doping amount (1.6 wt %), a large performance enhancement in permeability, aging resistance, and selectivity can be achieved. We rationalize this effect on the basis of the large surface to volume ratio of the filler, which leads to excellent dispersion at low concentrations and thus alters polymer packing. Although membranes based only on the polymer component age quickly with time, the performance of the resulting MOP-containing membranes meets the commercial target for postcombustion CO2 capture for more than 100 days.

The sub-nanometer beam of a helium ion microscope was used to study and optimize helium-ion beam induced deposition of PtC nanopillars with the (CH 3 ) 3 Pt(C P CH 3 ) precursor. The beam current, beam dwell time, precursor refresh time, and beam focus have been independently varied. Continuous beam exposure resulted in narrow but short pillars, while pulsed exposure resulted in thinner and higher ones. Furthermore, at short dwell times the deposition efficiency was very high, especially for a defocused beam. Efficiencies were measured up to 20 times the value for continuous exposure conditions. The interpretation of the experimental data was aided by a Monte Carlo simulation of the deposition. The results indicate that two regimes are operational in ion beam induced deposition (IBID). In the first one, the adsorbed precursor molecules originally present in the beam interaction region decompose. After the original precursor layer is consumed, further depletion is averted and growth continues by the supply of molecules via adsorption and surface diffusion. Depletion around the beam impact site can be distinguished from depletion on the flanges of the growing pillars. The Monte Carlo simulations for low precursor surface coverage reproduce measured growth rates, but predict considerably narrower pillars, especially at short dwell times. Both the experiments and the simulations show that the pillar width rapidly increases with increasing beam diameter. Optimal writing strategy, good beam focusing, and rapid beam positioning are needed for efficient and precise fabrication of extended and complex nanostructures by He-IBID.