Influence of the Surface Chemistry of Metal-Organic Polyhedra in Their Assembly into Ultrathin Films for Gas Separation.

The formation of ultrathin films of Rh-based porous metal-organic polyhedra (Rh-MOPs) by the Langmuir-Blodgett method has been explored. Homogeneous and dense monolayer films were formed at the air-water interface either using two different coordinatively alkyl-functionalized Rh-MOPs (HRhMOP(diz)12 and HRhMOP(oiz)12) or by in situ incorporation of aliphatic chains to the axial sites of dirhodium paddlewheels of another Rh-MOP (OHRhMOP) at the air-liquid interface. All these Rh-MOP monolayers were successively deposited onto different substrates in order to obtain multilayer films with controllable thicknesses. Aliphatic chains were partially removed from HRhMOP(diz)12 films post-synthetically by a simple acid treatment, resulting in a relevant modification of the film hydrophobicity. Moreover, the CO2/N2 separation performance of Rh-MOP-supported membranes was also evaluated, proving that they can be used as selective layers for efficient CO2 separation.

Green Preparation of Thin Films of Polybenzimidazole on Flat and Hollow Fiber Supports: Application to Hydrogen Separation.

This work shows the preparation of thin films, with thickness from 70 nm to 1 µm, of meta-polybenzimidazole (m-PBI) on polyimide P84 supports. Ethanolic solutions of m-PBI were used to coat flat and hollow fiber supports of asymmetric P84 with m-PBI in a process where the coating and drying was performed at room temperature. A solution of NaOH in EtOH allowed the dissolution of the m-PBI powder, providing the perfect coating solution to build thin films of m-PBI without damaging the polymeric support. It also meant a green alternative, avoiding the use of toxic solvents, such as dimethylacetamide. The resulting membranes have been tested for the separation of H2 mixtures at high temperature at different setups to allow checking their reproducibility. With 100 nm thickness the membranes showed their best gas separation performance. For flat membranes at 180 °C and 3 bar feed pressure a H2 permeance of 48.5 GPU was obtained, with respective H2 /CO2 and H2 /N2 selectivities of 33.3 and 55.8. Besides, the hollow fibers under a feed pressure of 6 bar and tested at the same temperature showed near 90 GPU of H2 with a H2 /CO2 selectivity of 13.5 in the one-fiber module and over 39 GPU of H2 with a H2 /CO2 selectivity of 20.2 in the five-fiber module. Finally, the stability of the membranes was proved for 22 days at 180 °C.

Pebax® 1041 supported membranes with carbon nanotubes prepared via phase inversion for CO2/N2 separation.

This work shows the preparation of Pebax® 1041 films from solutions in DMAc and water-DMAc emulsions as alternatives to those prepared by extrusion that can be found in the literature. These membranes were tested in post-combustion CO2 capture, in the separation of a 15/85 (v/v) CO2/N2 mixture. Self-supported membranes of Pebax® 1041 were prepared by solvent evaporation and phase inversion. The characterization of these films defined the intrinsic properties of this polymer in terms of chemical structure, crystallinity, thermal stability and gas separation performance (a CO2 permeability of 30 Barrer with a CO2/N2 selectivity of 21 at 35 °C and 3 bar feed pressure). Supported Pebax® 1041 membranes were also developed to decrease the Pebax® thickness (in the 1.5-10 µm range), resulting in a higher permeance. These membranes were prepared by a phase inversion process consisting of the precipitation of a Pebax® 1041/DMAc solution in water and dispersing it to form a stable emulsion that was drop-cast on PSF asymmetric supports. Once dried, the polymer formed a dense continuous layer. The phase inversion methodology is "greener" than solvent evaporation since dimethylacetamide is not released as toxic vapour during membrane preparation. The amount drop-cast led to a different selective layer thickness, which was enhanced by the dispersion of MWCNTs in the polymer emulsion. The properties of the Pebax® selective layer were studied by thermogravimetry and by measuring the contact angle of the membrane surface, and the optimal CO2/N2 selectivity (22.6) was obtained with a CO2 permeance of 3.0 GPU.

Ultrathin Films of Porous Metal-Organic Polyhedra for Gas Separation.

Ultrathin films of a robust RhII -based porous metal-organic polyhedra (MOP) have been obtained. Homogeneous and compact monolayer films (ca. 2.5 nm thick) were first formed at the air-water interface, deposited onto different substrates and characterized using spectroscopic methods, scanning transmission electron microscopy and atomic force microscopy. As a proof of concept, the gas separation performance of MOP-supported membranes has also been evaluated. Selective MOP ultrathin films (thickness ca. 60 nm) exhibit remarkable CO2 permeance and CO2 /N2 selectivity, demonstrating the great combined potential of MOP and Langmuir-based techniques in separation technologies.

Poly(ether-block-amide) copolymer membrane for CO2/N2 separation: the influence of the casting solution concentration on its morphology, thermal properties and gas separation performance.

The present work is focused on the study of the effect that the casting solution concentration has on the morphology and gas separation performance of poly(ether-block-amide) copolymer membranes (Pebax® MH 1657). With this aim, three different concentrations of Pebax® MH 1657 in the casting solution (1, 3 and 5 wt%) were used to prepare dense membranes with a thickness of 40 µm. The morphology and thermal stability of all membranes were characterized by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, rotational viscometry and thermogravimetric analyses. An increase in crystallinity was notable when the amount of solvent in the Pebax® MH 1657 solution was higher, mainly related to the polymer chains arrangement and the solvent evaporation time. Such characteristic seemed to play a key role in the thermal degradation of the membranes, confirming that the most crystalline materials tend to be thermally more stable than those with lower crystallinity. To study the influence of their morphology and operating temperature on the CO2 separation, gas separation tests were conducted with the gas mixture CO2/N2. Results indicated that a compromise must be found between the amount of solvent used to prepare the membranes and the crystallinity, in order to reach the best gas separation performance. In this study, the best performance was achieved with the membrane prepared from a 3 wt% casting solution, reaching at 35°C and under a feed pressure of 3 bar, a CO2 permeability of 110 Barrer and a CO2/N2 selectivity of 36.

Nanosheets of MIL-53(Al) applied in membranes with improved CO2/N2 and CO2/CH4 selectivities.

MIL-68(Al) and MIL-53(Al) are carboxylate-based metal-organic frameworks (MOFs) with the same chemical composition but different structures (polymorphs). In this study, MIL-53(Al) nanosheets of ca. 150 nm in size with an average thickness of 3.5 ± 0.9 nm were obtained after immersion of a sample composed of MIL-68(Al) and MIL-53(Al) in water under different conditions (ultrasound, stirring, reflux, 60 °C and room temperature). The disaggregated MIL-53(Al) nanosheets produced under more severe conditions were suspended in a PDMS solution and then deposited on asymmetric polyimide P84® supports under vacuum filtration to form supported mixed matrix membranes (MMMs). When applied to the separation of CO2/CH4 and CO2/N2 mixtures, the MMM with MIL-53(Al) nanosheets improved the CO2/CH4 (28.4-28.7 vs. 22.4) and CO2/N2 (19.9-23.2 vs. 17.5) selectivities of the conventional MIL-53(Al) MMM with higher CO2 permeances (20.8-29.6 GPU vs. 9.5 GPU for CO2/CH4 and 17.7-26.8 GPU vs. 11.2 GPU for CO2/N2).

The fabrication of ultrathin films and their gas separation performance from polymers of intrinsic microporosity with two-dimensional (2D) and three-dimensional (3D) chain conformations.

The expansion of the use of polymeric membranes in gas separation requires the development of membranes based on new polymers with improved properties and their assessment under real operating conditions. In particular, the fabrication of ultrathin films of high performance polymers that can be used as the selective layer in composite membranes will allow large reductions in the amount of the expensive polymer used and, hence, the cost of membrane fabrication. In this contribution, two polymers of intrinsic microporosity (PIMs) with very different chain configurations (two-dimensional, 2D, chains or conventional contorted three-dimensional, 3D, conformation) have been compared in their ability to form ultrathin films, showing the relevance of polymer design to obtain compact and defect-free films. Monolayers of the 2D polymer PIM-TMN-Trip can be efficiently deposited onto poly[1-(trimethylsilyl)-1-propyne] (PTMSP) to obtain composite membranes with a CO2/N2 selectivity similar to that of the corresponding thick membranes of the same PIM using only a small fraction of the selective polymer (less than 0.1%).

Synthesis of ZIF-93/11 Hybrid Nanoparticles via Post-Synthetic Modification of ZIF-93 and Their Use for H2 /CO2 Separation.

The present work shows the synthesis of nano-sized hybrid zeolitic imidazolate frameworks (ZIFs) with the rho topology based on a mixture of the linkers benzimidazole (bIm) and 4-methyl-5-imidazolecarboxaldehyde (4-m-5-ica). The hybrid ZIF was obtained by post-synthetic modification of ZIF-93 in a bIm solution. The use of different solvents, MeOH and N,N-dimethylacetamide (DMAc), and reaction times led to differences in the quantity of bIm incorporated to the framework, from 7.4 to 23 % according to solution-state NMR spectroscopy. XPS analysis showed that the mixture of linkers was also present at the surface of the particles. The inclusion of bIm to the ZIF-93 nanoparticles improved the thermal stability of the framework and also increased the hydrophobicity according to water adsorption results. N2 and CO2 adsorption experiments revealed that the hybrid material has an intermediate adsorption capacity, between those of ZIF-93 and ZIF-11. Finally, ZIF-93/11 hybrid materials were applied as fillers in polybenzimidazole (PBI) mixed matrix membranes (MMMs). These MMMs were used for H2 /CO2 separation (at 180 °C) reaching values of 207 Barrer of H2 and a H2 /CO2 selectivity of 7.7 that clearly surpassed the Robeson upper bound (corrected for this temperature).

Ultrathin Composite Polymeric Membranes for CO2 /N2 Separation with Minimum Thickness and High CO2 Permeance.

The use of ultrathin films as selective layers in composite membranes offers significant advantages in gas separation for increasing productivity while reducing the membrane size and energy costs. In this contribution, composite membranes have been obtained by the successive deposition of approximately 1 nm thick monolayers of a polymer of intrinsic microporosity (PIM) on top of dense membranes of the ultra-permeable poly[1-(trimethylsilyl)-1-propyne] (PTMSP). The ultrathin PIM films (30 nm in thickness) demonstrate CO2 permeance up to seven times higher than dense PIM membranes using only 0.04 % of the mass of PIM without a significant decrease in CO2 /N2 selectivity.