Vapor-Phase Synthesis of Electrocatalytic Covalent Organic Frameworks.

The inability to process many covalent organic frameworks (COFs) as thin films plagues their widespread utilization. Herein, a vapor-phase pathway for the bottom-up synthesis of a class of porphyrin-based COFs is presented. This approach allows integrating electrocatalysts made of metal-ion-containing COFs into the electrodes' architectures in a single-step synthesis and deposition. By precisely controlling the metal sites at the atomic level, remarkable electrocatalytic performance is achieved, resulting in unprecedentedly high mass activity values. How the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR-COFs is demonstrated. The theoretical data proves that the Cu site is highly active for nitrate conversion to ammonia on the synthesized COFs.

Correlating the Macrostructural Variations of an Ion Gel with Its Carbon Dioxide Sorption Capacity.

We report on a direct correlation between the macroscale structural variations and the gas sorption capacities of an ion gel. Here, we chose 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide ([Emim][TF2N]) and poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) as the ionic liquid and host polymer, respectively. The CO2 sorption in the thin films of the IL-polymer was measured using the gravimetric method. The results of our experiment showed that the trend in CO2 uptake of these mixtures was nonlinearly correlated with the content of IL. Here, we highlight that the variations in the molecular structure of the polymers were the main reason behind the observed trend. The presented data suggested the possibility of using the composition of mixtures containing IL and polymers to realize a synergistic gain for gas sorption in these mixtures.

One-Step Synthesis of Cationic Covalent Organic Frameworks.

Ionic covalent organic frameworks (iCOFs) have attractive properties that make them suitable for use as ion transport materials, as energy storage media, and for metal sorption. However, the synthetic pathways to prepare iCOFs are limited. Herein, we prepare an iCOF via a single-step reaction. The synthesized materials were isolated as polycrystalline nanowires. The theoretical and experimental data reveal that the synthesized iCOFs are predominately assembled into staggered configurations. The materials exhibit an uptake capacity of 3.5 g·g-1 for iodine. The ab initio calculations point to the role of bromide counterions, forming I2Br- as stable ions within the framework.

Thermo-Responsive Hydrophilic Support for Polyamide Thin-Film Composite Membranes with Competitive Nanofiltration Performance.

Poly(N-isopropylacrylamide) (PNIPAAm) was introduced into a polyethylene terephthalate (PET) nonwoven fabric to develop novel support for polyamide (PA) thin-film composite (TFC) membranes without using a microporous support layer. First, temperature-responsive PNIPAAm hydrogel was prepared by reactive pore-filling to adjust the pore size of non-woven fabric, creating hydrophilic support. The developed PET-based support was then used to fabricate PA TFC membranes via interfacial polymerization. SEM-EDX and AFM results confirmed the successful fabrication of hydrogel-integrated non-woven fabric and PA TFC membranes. The newly developed PA TFC membrane demonstrated an average water permeability of 1 L/m2 h bar, and an NaCl rejection of 47.0% at a low operating pressure of 1 bar. The thermo-responsive property of the prepared membrane was studied by measuring the water contact angle (WCA) below and above the lower critical solution temperature (LCST) of the PNIPAAm hydrogel. Results proved the thermo-responsive behavior of the prepared hydrogel-filled PET-supported PA TFC membrane and the ability to tune the membrane flux by changing the operating temperature was confirmed. Overall, this study provides a novel method to fabricate TFC membranes and helps to better understand the influence of the support layer on the separation performance of TFC membranes.

Multiphysics Modeling and Analysis of a Solar Desalination Process Based on Vacuum Membrane Distillation.

A hollow fiber vacuum membrane distillation (VMD) module was modeled using finite element analysis, and the results were used to conduct an exergy efficiency analysis for a solar-thermal desalination scheme. The performance of the VMD module was simulated under various operating conditions and membrane parameters. Membrane porosity, tortuosity, pore diameter, thickness, and fiber length were varied, along with feed temperature and feed configuration. In all cases, polarization phenomena were seen to inhibit the performance of the module. Under VMD operation, polarization of salt concentration was seen to be the main determining factor in the reduction of permeate flux. Within the boundary layer, salt concentration was seen to rapidly increase from the feed mass fraction of 0.035 to the saturation point. The increase in salt concentration led to a decrease in saturation pressure, the driving force for separation. Charging the feed into the shell instead of the lumen side of the membranes resulted in a further decrease in permeate flux. It is shown that adding a baffling scheme to the surface of the fibers can effectively reduce polarization phenomena and improve permeate flux. Increasing the overall recovery ratio was seen to increase the exergy efficiency of the system. Exergy efficiency was seen to have almost no dependency on membrane parameters due to the low recovery ratio in a single pass and the high heating duty required to reach the desired temperature for the feed stream.

Poly(Homopiperazine-Amide) Thin-Film Composite Membrane for Nanofiltration of Heavy Metal Ions.

The development of membrane-based technologies for the treatment of wastewater streams and resources containing heavy metal ions is in high demand. Among various technologies, nanofiltration (NF) membranes are attractive choices, and the continuous development of novel materials to improve the state-of-the-art NF membranes is highly desired. Here, we report on the synthesis of poly(homopiperazine-amide) thin-film composite (HTFC)-NF membranes, using homopiperazine (HP) as a monomer. The surface charge, hydrophilicity, morphology, cross-linking density, water permeation, solute rejection, and antifouling properties of the fabricated NF membranes were evaluated. The fabricated HTFC NF membranes demonstrated water permeability of 7.0 ± 0.3 L/(m2 h bar) and rejected Na2SO4, MgSO4, and NaCl with rejection values of 97.0 ± 0.6, 97.4 ± 0.5, and 23.3 ± 0.6%, respectively. The membranes exhibit high rejection values of 98.1 ± 0.3 and 96.3 ± 0.4% for Pb2+ and Cd2+ ions, respectively. The fouling experiment with humic acid followed by cross-flow washing of the membranes indicates that a flux recovery ratio (FRR) of 96.9 ± 0.4% can be obtained.

In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks.

Synthesis and processing of two- or three-dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electrochemical deposition of poly(5,10,15,20-tetrakis(4-aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. By adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py-POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.

Fabrication of Janus Membranes for Desalination of Oil-Contaminated Saline Water.

Desalination of oil-contaminated saline water using membrane distillation requires hydrophobic membranes with underwater superoleophobic surfaces. For designing such membranes, the chemistry and morphology of the interfacial domains in contact with the contaminated water need to be adjusted such that a stable water layer, adhering to the surface, prevents oil droplets from wetting the membrane. In this article, we present an approach that relies on the controlled functionalization of the surface of polyvinylidene fluoride (PVDF) membranes; we adjust the surface topography of the membranes and introduce chemical heterogeneity to them. We show that the morphology of the PVDF surface can be altered by adjusting the composition of the nonsolvent bath used for the phase inversion process. Also, we render the surface of the membranes hydrophilic by using an alkaline chemical bath solution. The membrane morphology and effectiveness of our chemical treatment were confirmed by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), Fourier-transformed infrared spectroscopy (FTIR), and zeta potential measurements. A stable underwater contact angle, higher than 150°, was observed for both canola oil (ρ ≈ 0.913 g cm-3, γ ≈ 31.5 mN m-1) and hexane (ρ ≈ 0.655 g cm-3, γ ≈ 18 mN m-1). We evaluated the performance of both pristine and functionalized membranes in a laboratory-scale direct contact membrane distillation (DCMD) setup and desalinated a saline solution contaminated with 500 ppm canola oil. Our results show that oil does not wet the functionalized membrane during the desalination process. The average permeate flux and salt rejection values for the functionalized membranes were 45 ± 5 Lm-2h-1 ( Tfeed = 70 °C, Tdistillate = 20 °C) and 99.99%, respectively.

Highly stiff yet elastic microcapsules incorporating cellulose nanofibrils.

Microcapsules with high mechanical stability and elasticity are desirable in a variety of contexts. We report a single-step method to fabricate such microcapsules by microfluidic interfacial complexation between high stiffness cellulose nanofibrils (CNF) and an oil-soluble cationic random copolymer. Single-capsule compression measurements reveal an elastic modulus of 53 MPa for the CNF-based capsule shell with complete recovery of deformation from strains as large as 19%. We demonstrate the ability to manipulate the shell modulus by the use of polyacrylic acid (PAA) as a binder material, and observe a direct relationship between the shell modulus and the PAA concentration, with moduli as large as 0.5 GPa attained. These results demonstrate that CNF incorporation provides a facile route for producing strong yet flexible microcapsule shells.

Thin Polymer Films with Continuous Vertically Aligned 1 nm Pores Fabricated by Soft Confinement.

Membrane separations are critically important in areas ranging from health care and analytical chemistry to bioprocessing and water purification. An ideal nanoporous membrane would consist of a thin film with physically continuous and vertically aligned nanopores and would display a narrow distribution of pore sizes. However, the current state of the art departs considerably from this ideal and is beset by intrinsic trade-offs between permeability and selectivity. We demonstrate an effective and scalable method to fabricate polymer films with ideal membrane morphologies consisting of submicron thickness films with physically continuous and vertically aligned 1 nm pores. The approach is based on soft confinement to control the orientation of a cross-linkable mesophase in which the pores are produced by self-assembly. The scalability, exceptional ease of fabrication, and potential to create a new class of nanofiltration membranes stand out as compelling aspects.

Guided Evolution of Bulk Metallic Glass Nanostructures: A Platform for Designing 3D Electrocatalytic Surfaces.

Electrochemical devices such as fuel cells, electrolyzers, lithium-air batteries, and pseudocapacitors are expected to play a major role in energy conversion/storage in the near future. Here, it is demonstrated how desirable bulk metallic glass compositions can be obtained using a combinatorial approach and it is shown that these alloys can serve as a platform technology for a wide variety of electrochemical applications through several surface modification techniques.

Elements Provide a Clue: Nanoscale Characterization of Thin-Film Composite Polyamide Membranes.

In this study, we exploit the nitrogen-sulfur elemental contrast of thin-film composite (TFC) polyamide membranes and present, for the first time, the application of two elemental analysis techniques, scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDX) and X-ray photoelectron spectroscopy (XPS) C60+ ion-beam sputtering, to elucidate the nanoscale structure and chemical composition of the polyamide-polysulfone interface. Although STEM-EDX elemental mapping depicts the presence of a dense polyamide layer at the interface, it is incapable of resolving the elemental contrast at nanoscale resolution at the interfacial zone. Depth-resolved XPS C60+ ion-beam sputtering enabled nanoscale characterization of the polyamide-polysulfone interface and revealed the presence of a heterogeneous layer that contains both polyamide and polysulfone signatures. Our results have important implications for future studies to elucidate the structure-property-performance relationship of TFC membranes.

Soft microcapsules with highly plastic shells formed by interfacial polyelectrolyte-nanoparticle complexation.

Composite microcapsules have been aggressively pursued as designed chemical entities for biomedical and other applications. Common preparations rely on multi-step, time consuming processes. Here, we present a single-step approach to fabricate such microcapsules with shells composed of nanoparticle-polyelectrolyte and protein-polyelectrolyte complexes, and demonstrate control of the mechanical and release properties of these constructs. Interfacial polyelectrolyte-nanoparticle and polyelectrolyte-protein complexation across a water-oil droplet interface results in the formation of capsules with shell thicknesses of a few µm. Silica shell microcapsules exhibited a significant plastic response at small deformations, whereas lysozyme incorporated shells displayed a more elastic response. We exploit the plasticity of nanoparticle incorporated shells to produce microcapsules with high aspect ratio protrusions by micropipette aspiration.

Antimicrobial Properties of Graphene Oxide Nanosheets: Why Size Matters.

Graphene oxide (GO) is a promising material for the development of antimicrobial surfaces due to its contact-based antimicrobial activity. However, the relationship between GO physicochemical properties and its antimicrobial activity has yet to be elucidated. In this study, we investigated the size-dependency of GO antimicrobial activity using the Gram-negative bacteria Escherichia coli. GO suspensions of average sheet area ranging from 0.01 to 0.65 µm(2) were produced and their antimicrobial activity evaluated in cell suspensions or as a model GO surface coating. The antimicrobial activity of GO surface coatings increased 4-fold when GO sheet area decreased from 0.65 to 0.01 µm(2). The higher antimicrobial effect of smaller GO sheets is attributed to oxidative mechanisms associated with the higher defect density of smaller sheets. In contrast, in suspension assays, GO interacted with bacteria in a cell entrapment mechanism; in this case, the antimicrobial effect of GO increased with increasing sheet area, with apparent complete inactivation observed for the 0.65 µm(2) sheets after a 3 h exposure. However, cell inactivation by GO entrapment was reversible and all initially viable cells could be recovered when separated from GO sheets by sonication. These findings provide useful guidelines for future development of graphene-based antimicrobial surface coatings, where smaller sheet sizes can increase the antimicrobial activity of the material. Our study further emphasizes the importance of an accurate assessment of the antimicrobial effect of nanomaterials when used for antimicrobial surface design.

Polarization screening-induced magnetic phase gradients at complex oxide interfaces.

Thin-film oxide heterostructures show great potential for use in spintronic memories, where electronic charge and spin are coupled to transport information. Here we use a La0.7Sr0.3MnO3 (LSMO)/PbZr0.2Ti0.8O3 (PZT) model system to explore how local variations in electronic and magnetic phases mediate this coupling. We present direct, local measurements of valence, ferroelectric polarization and magnetization, from which we map the phases at the LSMO/PZT interface. We combine these experimental results with electronic structure calculations to elucidate the microscopic interactions governing the interfacial response of this system. We observe a magnetic asymmetry at the LSMO/PZT interface that depends on the local PZT polarization and gives rise to gradients in local magnetic moments; this is associated with a metal-insulator transition at the interface, which results in significantly different charge-transfer screening lengths. This study establishes a framework to understand the fundamental asymmetries of magnetoelectric coupling in oxide heterostructures.

Highly conductive single-walled carbon nanotube thin film preparation by direct alignment on substrates from water dispersions.

A safe, scalable method for producing highly conductive aligned films of single-walled carbon nanotubes (SWNTs) from water suspensions is presented. While microfluidic assembly of SWNTs has received significant attention, achieving desirable SWNT dispersion and morphology in fluids without an insulating surfactant or toxic superacid is challenging. We present a method that uniquely produces a noncorrosive ink that can be directly applied to a device in situ, which is different from previous fabrication techniques. Functionalized SWNTs (f-SWNTs) are dispersed in an aqueous urea solution to leverage binding between the amine group of urea and the carboxylic acid group of f-SWNTs and obtain urea-SWNT. Compared with SWNTs dispersed using conventional methods (e.g., superacid and surfactants), the dispersed urea-SWNT aggregates have a higher aspect ratio with a rodlike morphology as measured by light scattering. The Mayer rod technique is used to prepare urea-SWNT, highly aligned films (two-dimensional nematic order parameter of 0.6, 5 µm spot size, via polarized Raman) with resistance values as low as 15-1700 Ω/sq in a transmittance range of 2-80% at 550 nm. These values compete with the best literature values for conductivity of SWNT-enabled thin films. The findings offer promising opportunities for industrial applications relying on highly conductive thin SWNT films.

Scalable fabrication of polymer membranes with vertically aligned 1 nm pores by magnetic field directed self-assembly.

There is long-standing interest in developing membranes possessing uniform pores with dimensions in the range of 1 nm and physical continuity in the macroscopic transport direction to meet the needs of challenging small molecule and ionic separations. Here we report facile, scalabe fabrication of polymer membranes with vertically (i.e., along the through-plane direction) aligned 1 nm pores by magnetic-field alignment and subsequent cross-linking of a liquid crystalline mesophase. We utilize a wedge-shaped amphiphilic species as the building block of a thermotropic columnar mesophase with 1 nm ionic nanochannels, and leverage the magnetic anisotropy of the amphiphile to control the alignment of these pores with a magnetic field. In situ X-ray scattering and subsequent optical microscopy reveal the formation of highly ordered nanostructured mesophases and cross-linked polymer films with orientational order parameters of ca. 0.95. High-resolution transmission electron microscopy (TEM) imaging provides direct visualization of long-range persistence of vertically aligned, hexagonally packed nanopores in unprecedented detail, demonstrating high-fidelity retention of structure and alignment after photo-cross-linking. Ionic conductivity measurements on the aligned membranes show a remarkable 85-fold enhancement of conductivity over nonaligned samples. These results provide a path to achieving the large area control of morphology and related enhancement of properties required for high-performance membranes and other applications.

Role of HF in oxygen removal from carbon nanotubes: implications for high performance carbon electronics.

Oxygen removal from SWNTs is crucial for many carbon electronic devices. This work shows that HF treatment followed by current stimulation is a very effective method for oxygen removal. Using a procedure involving HF treatment, current stimulation and spin-casting AgNWs onto a SWNT thin film, record high efficiency SWNT/p-Si solar cells have been developed.

Single-step microfluidic fabrication of soft monodisperse polyelectrolyte microcapsules by interfacial complexation.

Common methods for fabrication of polyelectrolyte microcapsules rely on a multi-step process. We propose a single-step approach to generate polyelectrolyte microcapsules with 1-2 µm shells based on polyelectrolyte complexation across a water/oil droplet interface and study the effect of parameters controlling the polyelectrolyte complexation on shell thickness.

In situ formation of silver nanoparticles on thin-film composite reverse osmosis membranes for biofouling mitigation.

The potential to incorporate silver nanoparticles (Ag-NPs) as biocides in membranes for water purification has gained much interest in recent years. However, a viable strategy for loading the Ag-NPs on the membrane remains challenging. This paper presents a novel, facile procedure for loading Ag-NPs on thin-film composite (TFC) reverse osmosis membranes. Reaction of silver salt with a reducing agent on the membrane surface resulted in uniform coverage of Ag-NPs, irreversibly bound to the membrane, as confirmed by XPS, TEM, and SEM analyses. Salt selectivity of the membrane as well its surface roughness, hydrophilicity, and zeta potential were not impacted by Ag-NP functionalization, while a slight reduction (up to 17%) in water permeability was observed. The formed Ag-NPs imparted strong antibacterial activity to the membrane, leading to reduction of more than 75% in the number of live bacteria attached to the membrane for three model bacteria strains. In addition, confocal microscopy analyses revealed that Ag-NPs significantly suppressed biofilm formation, with 41% reduction in total biovolume and significant reduction in EPS, dead, and live bacteria on the functionalized membrane. The simplicity of the method, the short reaction time, the ability to load the Ag-NPs on site, and the strong imparted antibacterial activity highlight the potential of this method in real-world RO membrane applications.