Luis Francisco Villalobos

A Metal Chelating Porous Polymeric Support: The Missing Link for a Defect-free Metal-Organic Framework Composite Membrane

Since the discovery of size-selective metal-organic frameworks (MOFs), researchers have tried to incorporate these materials into gas separation membranes. Impressive gas selectivities were found, but these MOF membranes were mostly made on inorganic supports, which are generally too bulky and expensive for industrial gas separation. Forming MOF layers on porous polymer supports is industrially attractive but technically challenging. Two features to overcome these problems are described: 1) a metal chelating support polymer to bind the MOF layer, and 2) control of MOF crystal growth by contra-diffusion, aiming at a very thin nanocrystalline MOF layer. Using a metal chelating poly-thiosemicarbazide (PTSC) support and adjusting the metal and organic ligand concentrations carefully, a very compact ZIF-8 (ZIF=zeolitic imidazolate framework) layer was produced that displayed interference colors because of its smooth surface and extreme thinness-within the range of visible light. High performances were measured in terms of hydrogen/propane (8350) and propylene/propane (150) selectivity.

Complexation-Induced Phase Separation: Preparation of Composite Membranes with a Nanometer-Thin Dense Skin Loaded with Metal Ions

We present the development of a facile phase-inversion method for forming asymmetric membranes with a precise high metal ion loading capacity in only the dense layer. The approach combines the use of macromolecule-metal intermolecular complexes to form the dense layer of asymmetric membranes with nonsolvent-induced phase separation to form the porous support. This allows the independent optimization of both the dense layer and porous support while maintaining the simplicity of a phase-inversion process. Moreover, it facilitates control over (i) the thickness of the dense layer throughout several orders of magnitude from less than 15 nm to more than 6 μm, (ii) the type and amount of metal ions loaded in the dense layer, (iii) the morphology of the membrane surface, and (iv) the porosity and structure of the support. This simple and scalable process provides a new platform for building multifunctional membranes with a high loading of well-dispersed metal ions in the dense layer.

Cyclodextrin Films with Fast Solvent Transport and Shape-Selective Permeability

This study describes the molecular-level design of a new type of filtration membrane made of crosslinked cyclodextrins-inexpensive macrocycles of glucose, shaped like hollow truncated cones. The channel-like cavities of cyclodextrins spawn numerous paths of defined aperture in the separation layer that can effectively discriminate between molecules. The transport of molecules through these membranes is highly shape-sensitive. In addition, the presence of hydrophobic (cavity) and hydrophilic (ester-crosslinked outer part) domains in these films results in high permeances for both polar and nonpolar solvents.

Polymer and Membrane Design for Low Temperature Catalytic Reactions

Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membranes ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed.

Graphene oxide doped ionic liquid ultrathin composite membranes for efficient CO2 capture

Advanced membrane systems with high flux and sufficient selectivity are required for industrial gas separation processes. In order to achieve high flux and high selectivity, the membrane material should be as thin as possible and it should have selective sieving channels and long term stability. This could be achieved by designing a three component material consisting of a blend of an ionic liquid and graphene oxide covered by a highly permeable low selective polymeric coating. By using a simple dip coating technique, we prepared high flux and CO2 selective ultrathin graphene oxide (GO)/ionic liquid membranes on a porous ultrafiltration support. The ultrathin composite membranes derived from GO/ionic liquid complex displays remarkable combinations of permeability (CO2 flux: 37 GPU) and selectivity (CO2/N2 selectivity: 130) that surpass the upper bound of ionic liquid membranes for CO2/N2 separation. Moreover, the membranes were stable when tested for 120 hours.

Antibiofilm effect enhanced by modification of 1,2,3-triazole and palladium nanoparticles on polysulfone membranes

Biofouling impedes the performance of membrane bioreactors. In this study, we investigated the antifouling effects of polysulfone membranes that were modified by 1,2,3-triazole and palladium (Pd) nanoparticles. The modified membranes were evaluated for antibacterial and antifouling efficacy in a monoculture species biofilm (i.e., drip flow biofilm reactor, DFR) and mixed species biofilm experiment (i.e., aerobic membrane reactor, AeMBR). 1,2,3-triazole and Pd nanoparticles inhibited growth of Pseudomonas aeruginosa in both aerobic and anaerobic conditions. The decrease in bacterial growth was observed along with a decrease in the amount of total polysaccharide within the monoculture species biofilm matrix. When the modified membranes were connected to AeMBR, the increase in transmembrane pressure was lower than that of the non-modified membranes. This was accompanied by a decrease in protein and polysaccharide concentrations within the mixed species biofilm matrix. Biomass amount in the biofilm layer was also lower in the presence of modified membranes, and there was no detrimental effect on the performance of the reactor as evaluated from the nutrient removal rates. 16S rRNA analysis further attributed the delay in membrane fouling to the decrease in relative abundance of selected bacterial groups. These observations collectively point to a lower fouling occurrence achieved by the modified membranes.

In situ growth of biocidal AgCl crystals in the top layer of asymmetric polytriazole membranes

Scalable fabrication strategies to concentrate biocidal materials in only the surface of membranes are highly desirable. In this letter, tight-UF polytriazole membranes with a high concentration of biocide silver chloride (AgCl) crystals dispersed in only their top layer are presented. They were made following a simple dual-bath process that is compatible with current commercial membrane casting facilities. These membranes can achieve a 150-fold increase in their antimicrobial character compared to their silver-free counterpart. Moreover, fine-tuning of their properties is straightforward. A change in the silver concentration in one of the baths is sufficient to tune the permeance, molecular weight cut-off (MWCO) and silver loading of the final membrane.

Polybenzimidazole-based mixed membranes with exceptionally high water vapor permeability and selectivity

Polybenzimidazole (PBI), a thermally and chemically stable polymer, is commonly used to fabricate membranes for applications like hydrogen recovery at temperatures of more than 300 °C, fuel cells working in a highly acidic environment, and nanofiltration in aggressive solvents. This report shows for the first time the use of PBI dense membranes for water vapor/gas separation applications. They showed an excellent selectivity and high water vapor permeability. The incorporation of inorganic hydrophilic titanium-based nano-fillers into the PBI matrix further increased the water vapor permeability and water vapor/N2 selectivity. The most selective mixed matrix membrane with 0.5 wt% loading of TiO2 nanotubes yielded a water vapor permeability of 6.8 × 104 barrer and a H2O/N2 selectivity of 3.9 × 106. The most permeable membrane with 1 wt% loading of carboxylated TiO2 nanoparticles had a water vapor permeability of 7.1 × 104 barrer and a H2O/N2 selectivity of 3.1 × 106. The performance of these membranes in terms of water vapor transport and selectivity is among the highest reported ones. The remarkable ability of PBI to efficiently permeate water versus other gases opens the possibility to fabricate membranes for the dehumidification of streams in harsh environments. This includes the removal of water from high temperature reaction mixtures to shift the equilibrium towards products.

Embedding 1D Conducting Channels into 3D Isoporous Polymer Films for High-Performance Humidity Sensing

Isoporous block copolymer (BCP) films have received exponential interest as highly selective membranes, stemming from their unique morphological features, but their applications in functional devices remain to be realized. Now single-walled carbon nanotubes (CNTs) were efficiently incorporated into isoporous block copolymer films for chemiresistive sensing at room temperature. Leveraging the efficient charge extraction ability of CNTs together with nanochannel arrays aligned perpendicular to the surface of the films, an ultrafast response time of 0.3 s was achieved for humidity detection with a sensor response of about 800 on changing humidity from 10 % to 95 %. Furthermore, the sensor also responds to various organic vapors, underscoring its promising detection capability.