Enhancing Membrane Materials for Efficient Li Recycling and Recovery.

Rapid uptake of lithium-centric technology, e.g., electric vehicles and large-scale energy storage, is increasing the demand for efficient technologies for lithium extraction from aqueous sources.

Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin-based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co-crystallisation of tetraphenylporphyrin (TPP) with octa(2',6'-di-iso-propylphenoxy)phthalocyanine or some of its metal complexes [(dipPhO)PcM; M=H, Al-OH, Ti=O, Mn-Cl, Fe-Cl, Co, Ni, Cu, Zn, Ga-Cl, Ag, In-Cl or Au-Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)PcM, which is driven by the complementary shape and symmetry of the two macrocycles.

Selective ion transport through hydrated micropores in polymer membranes.

Ion-conducting polymer membranes are essential in many separation processes and electrochemical devices, including electrodialysis, redox flow batteries, fuel cells and electrolysers. Controlling ion transport and selectivity in these membranes largely hinges on the manipulation of pore size. Although membrane pore structures can be designed in the dry state, they are redefined upon hydration owing to swelling in electrolyte solutions.

Ligand effects on gas adsorption in nanoporous phthalocyanine crystals.

X-ray diffraction is used to study the sorption of CO and NO in two phthalocyanine nanoporous crystals (PNCs) with 4,4' bipyridine or 4,4' bipyrimidine coordinated to open Co sites, demonstrating how the coordinated ligands influence the gas sorption properties and structures of the PNCs.

Triptycene-like naphthopleiadene as a readily accessible scaffold for supramolecular and materials chemistry.

Triptycene derivatives are used extensively in supramolecular and materials chemistry, however, most are prepared using a multi-step synthesis involving the generation of a benzyne intermediate, which hinders production on a large scale. Inspired by the ease of the synthesis of resorcinarenes, we report the rapid and efficient preparation of triptycene-like 1,6,2',7'-tetrahydroxynaphthopleiadene directly from 2,7-dihydroxynaphthalene and phthalaldehyde. Structural characterisation confirms the novel bridged bicyclic framework, within which the planes of the single benzene ring and two naphthalene units are fixed at an angle of ∼120° relative to each other.

Triphasic Oxygen Storage in Wet Nanoparticulate Polymer of Intrinsic Microporosity (PIM-1) on Platinum: An Electrochemical Investigation.

The triphasic interaction of gases with electrode surfaces immersed in aqueous electrolyte is crucial in electrochemical technologies (fuel cells, batteries, sensors). Some microporous materials modify this interaction locally via triphasic storage capacity for gases in aqueous environments linked to changes in apparent oxygen concentration and diffusivity (as well as activity and reactivity). Here, a nanoparticulate polymer of intrinsic microporosity (PIM-1) in aqueous electrolyte is shown to store oxygen gas and thereby enhance electrochemical signals for oxygen reduction in aqueous media.

Microscopic molecular mobility of high-performance polymers of intrinsic microporosity revealed by neutron scattering - bend fluctuations and signature of methyl group rotation.

Polymers of intrinsic microporosity exhibit a combination of high gas permeability and reasonable permselectivity, which makes them attractive candidates for gas separation membrane materials. The diffusional selective gas transport properties are connected to the molecular mobility of these polymers in the condensed state. Incoherent quasielastic neutron scattering was carried out on two polymers of intrinsic microporosity, PIM-EA-TB(CH) and its demethylated counterpart PIM-EA-TB(H), which have high Brunauer-Emmett-Teller surface area values of 1030 m g and 836 m g, respectively.

Tuning and Coupling Irreversible Electroosmotic Water Flow in Ionic Diodes: Methylation of an Intrinsically Microporous Polyamine (PIM-EA-TB).

Molecularly rigid polymers with internal charges (positive charges induced by amine methylation) allow electroosmotic water flow to be tuned by adjusting the charge density (the degree of methylation). Here, a microporous polyamine (PIM-EA-TB) is methylated to give a molecularly rigid anion conductor. The electroosmotic drag coefficient (the number of water molecules transported per anion) is shown to increase with a lower degree of methylation.

Nanophase-photocatalysis: loading, storing, and release of HO using graphitic carbon nitride.

A blue light mediated photochemical process using solid graphitic carbon nitride (g-CN) in ambient air/isopropanol vapour is suggested to be linked to "nanophase" water inclusions and is shown to produce approx. 50 μmol HO per gram of g-CN, which can be stored in the solid g-CN for later release for applications, for example, in disinfection or anti-bacterial surfaces.

Thin Film Composite Membranes with Regulated Crossover and Water Migration for Long-Life Aqueous Redox Flow Batteries.

Redox flow batteries (RFBs) are promising for large-scale long-duration energy storage owing to their inherent safety, decoupled power and energy, high efficiency, and longevity. Membranes constitute an important component that affects mass transport processes in RFBs, including ion transport, redox-species crossover, and the net volumetric transfer of supporting electrolytes. Hydrophilic microporous polymers, such as polymers of intrinsic microporosity (PIM), are demonstrated as next-generation ion-selective membranes in RFBs.

Near-frictionless ion transport within triazine framework membranes.

The enhancement of separation processes and electrochemical technologies such as water electrolysers, fuel cells, redox flow batteries and ion-capture electrodialysis depends on the development of low-resistance and high-selectivity ion-transport membranes. The transport of ions through these membranes depends on the overall energy barriers imposed by the collective interplay of pore architecture and pore-analyte interaction. However, it remains challenging to design efficient, scaleable and low-cost selective ion-transport membranes that provide ion channels for low-energy-barrier transport.

ECL sensor for selective determination of citrate ions as a prostate cancer biomarker using polymer of intrinsic microporosity-1 nanoparticles/nitrogen-doped carbon quantum dots.

Urine citrate analysis is relevant in the screening and monitoring of patients with prostate cancer and calcium nephrolithiasis. A sensitive, fast, easy, and low-maintenance electrochemiluminescence (ECL) method with conductivity detection for the analysis of citrate in urine is developed and validated by employing polymer of intrinsic microporosity-1 nanoparticles/nitrogen-doped carbon quantum dots (nano-PIM-1/N-CQDs). Using optimum conditions, the sensor was applied in ECL experiments in the presence of different concentrations of citrate ions.

Ion-Selective Microporous Polymer Membranes with Hydrogen-Bond and Salt-Bridge Networks for Aqueous Organic Redox Flow Batteries.

Redox flow batteries (RFBs) have great potential for long-duration grid-scale energy storage. Ion-conducting membranes are a crucial component in RFBs, allowing charge-carrying ions to transport while preventing the cross-mixing of redox couples. Commercial Nafion membranes are widely used in RFBs, but their unsatisfactory ionic and molecular selectivity, as well as high costs, limit the performance and the widespread deployment of this technology.

Dibenzomethanopentacene-Based Polymers of Intrinsic Microporosity for Use in Gas-Separation Membranes.

Dibenzomethanopentacene (DBMP) is shown to be a useful structural component for making Polymers of Intrinsic Microporosity (PIMs) with promise for making efficient membranes for gas separations. DBMP-based monomers for PIMs are readily prepared using a Diels-Alder reaction between 2,3-dimethoxyanthracene and norbornadiene as the key synthetic step. Compared to date for the archetypal PIM-1, the incorporation of DBMP simultaneously enhances both gas permeability and the ideal selectivity for one gas over another.

2,2'-Biphenol-based Ultrathin Microporous Nanofilms for Highly Efficient Molecular Sieving Separation.

Organic solvent nanofiltration (OSN) is an emerging membrane separation technology, which urgently requires robust, easily processed, OSN membranes possessing high permeance and small solutes-selectivity to facilitate enhanced industrial uptake. Herein, we describe the use of two 2,2'-biphenol (BIPOL) derivatives to fabricate hyper-crosslinked, microporous polymer nanofilms through IP. Ultra-thin, defect-free polyesteramide/polyester nanofilms (≈5 nm) could be obtained readily due to the relatively large molecular size and ionized nature of the BIPOL monomers retarding the rate of the IP.

Thin Film Composite Membranes Based on the Polymer of Intrinsic Microporosity PIM-EA(Me)-TB Blended with Matrimid5218.

In this work, thin film composite (TFC) membranes were fabricated with the selective layer based on a blend of polyimide Matrimid5218 and polymer of intrinsic microporosity (PIM) composed of Tröger's base, TB, and dimethylethanoanthracene units, PIM-EA(Me)-TB. The TFCs were prepared with different ratios of the two polymers and the effect of the PIM content in the blend of the gas transport properties was studied for pure He, H, O, N, CH, and CO using the well-known time lag method. The prepared TFC membranes were further characterized by IR spectroscopy and scanning electron microscopy (SEM).

Solution-Processable Redox-Active Polymers of Intrinsic Microporosity for Electrochemical Energy Storage.

Redox-active organic materials have emerged as promising alternatives to conventional inorganic electrode materials in electrochemical devices for energy storage. However, the deployment of redox-active organic materials in practical lithium-ion battery devices is hindered by their undesired solubility in electrolyte solvents, sluggish charge transfer and mass transport, as well as processing complexity. Here, we report a new molecular engineering approach to prepare redox-active polymers of intrinsic microporosity (PIMs) that possess an open network of subnanometer pores and abundant accessible carbonyl-based redox sites for fast lithium-ion transport and storage.

Long-Life Aqueous Organic Redox Flow Batteries Enabled by Amidoxime-Functionalized Ion-Selective Polymer Membranes.

Redox flow batteries (RFBs) based on aqueous organic electrolytes are a promising technology for safe and cost-effective large-scale electrical energy storage. Membrane separators are a key component in RFBs, allowing fast conduction of charge-carrier ions but minimizing the cross-over of redox-active species. Here, we report the molecular engineering of amidoxime-functionalized Polymers of Intrinsic Microporosity (AO-PIMs) by tuning their polymer chain topology and pore architecture to optimize membrane ion transport functions.

Development of efficient aqueous organic redox flow batteries using ion-sieving sulfonated polymer membranes.

Redox flow batteries using aqueous organic-based electrolytes are promising candidates for developing cost-effective grid-scale energy storage devices. However, a significant drawback of these batteries is the cross-mixing of active species through the membrane, which causes battery performance degradation. To overcome this issue, here we report size-selective ion-exchange membranes prepared by sulfonation of a spirobifluorene-based microporous polymer and demonstrate their efficient ion sieving functions in flow batteries.

Catechin or quercetin guests in an intrinsically microporous polyamine (PIM-EA-TB) host: accumulation, reactivity, and release.

Microporous polymer materials based on molecularly "stiff" structures provide intrinsic microporosity, typical micropore sizes of 0.5 nm to 1.5 nm, and the ability to bind guest species.

Effects of g-CN Heterogenization into Intrinsically Microporous Polymers on the Photocatalytic Generation of Hydrogen Peroxide.

Graphitic carbon nitride (g-CN) is known to photogenerate hydrogen peroxide in the presence of hole quenchers in aqueous environments. Here, the g-CN photocatalyst is embedded into a host polymer of intrinsic microporosity (PIM-1) to provide recoverable heterogenized photocatalysts without loss of activity. Different types of g-CN (including Pt@g-CN, Pd@g-CN, and Au@g-CN) and different quenchers are investigated.

Non-enzymatic electrochemical cholesterol sensor based on strong host-guest interactions with a polymer of intrinsic microporosity (PIM) with DFT study.

Advances in materials science have accelerated the development of diagnostic tools with the last decade witnessing the development of enzyme-free sensors, owing to the improved stability, low cost and simple fabrication of component materials. However, the specificity of non-enzymatic sensors for certain analytes still represents a challenging task, for example the determination of cholesterol level in blood is vital due to its medical relevance. In this work, a reagent displacement assay for cholesterol sensing in serum samples was developed.

Control Over the Morphology of Electrospun Microfibrous Mats of a Polymer of Intrinsic Microporosity.

This study reports for the first time the preparation of an electrospun microfibrous mat of PIM-EA-TB. The electrospinning was carried out using a chloroform/-Propyl-lactate (n-PL) binary solvent system with different chloroform/nPL ratios, in order to control the morphology of the microfibres. With pure chloroform, porous and dumbbell shape fibres were obtained whereas, with the addition on n-PL, circular and thinner fibres have been produced due to the higher boiling point and the higher conductivity of n-PL.

Polymers of Intrinsic Microporosity in the Design of Electrochemical Multicomponent and Multiphase Interfaces.

Polymers of intrinsic microporosity (or PIMs) provide porous materials due to their highly contorted and rigid macromolecular structures, which prevent space-efficient packing. PIMs are readily dissolved in solvents and can be cast into robust microporous coatings and membranes. With a typical micropore size range of around 1 nm and a typical surface area of 700-1000 m g, PIMs offer channels for ion/molecular transport and pores for gaseous species, solids, and liquids to coexist.