Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol

Intrinsically microporous polyamines (PIM-EA-TB) provide tertiary amine binding sites for protons and in this way allow switching/gating from a low ionic conductivity state to semipermeable anion conductivity through micropores. In ethanolic NaClO4 media ionic conductivity in PIM-EA-TB films (approx. 10 μm thick; deposited asymmetrically onto a 10 μm diameter microhole in 5 μm thick Teflon) is lowered by ion exclusion compared to conductivity observed in aqueous environments. However, in the presence of protons in ethanol PIM-EA-TB films are shown to switch from essentially insulating to anionic diode behaviour. Similar observations are reported for Cu2+ but not for other types of cations such as Na+, K+, Mg2+ (all as perchlorate salts). Binding constants are evaluated, and protonation is identified to cause gating for both H+ and Cu2+. Both chemical and electrochemical gating/switching is demonstrated by placing a platinum electrode close to the PIM-EA-TB film and applying positive or negative bias to locally generate acid/base

Hydrogen-Mediated Photoelectrocatalysis with Nickel-Modified Poly(Heptazine Imides)

Polymeric carbon nitrides (C3N4) are photochemically active organic semiconductors that can be produced in a wide range of structural types. Here, a poly-(heptazine imide) containing nickel single atoms (Ni-PHI) is employed for photochemical hydrogen production and is compared to the non-nickel-doped semiconductor. Film deposits are formed on a platinum disk electrode (to detect hydrogen) and a coating of the molecularly rigid polymer of intrinsic microporosity PIM-1 is applied to (i) mechanically stabilize the photo-catalyst film without impeding photocatalysis and (ii) assist in the interfacial hydrogen capture/oxygen suppression process. In the presence of hole quenchers such as methanol or ethanol, anodic photocurrents linked to hydrogen production/oxidation are observed. A comparison with an experiment on glassy carbon confirms the formation of interfacial hydrogen as a mediator. The effects of hole quencher concentration are evaluated. The system Pt/Ni-PHI/PIM-1 is employed in a single-compartment photo-fuel cell

Novel CO2-philic porous organic polymers synthesized in water: a leap towards eco-sustainability

We introduce two novel keto-enamine-linked porous organic polymers (POPs) distinguished by the presence of methyl or ethyl groups in their triamine precursors. These innovative POPs can be synthesized efficiently in water under mild conditions, utilizing starting materials that can be prepared on a gram scale through well-established procedures. Unlike most CO2-philic POPs, which often require organic solvents, high temperatures, catalysts, additives, or hydrothermal equipment, these new polymers are synthesized in pure water at a relatively low temperature (70 °C) without any catalysts or additives and using common glassware. The N-rich composition of these porous organic polymers also contributes to their high adsorption selectivity for CO2 over N2, as calculated with the IAST method at 298 K. This combination of environmentally friendly synthesis, high yield, and superior adsorption properties positions these novel POPs as promising candidates for greener carbon capture technologies based on solid sorbents

Ultrasonic-assisted removal of cationic and anionic dyes residues from wastewater using functionalized triptycene-based polymers of intrinsic microporosity (PIMs)

In this work, a series of hypercrosslinked polymers of intrinsic microporosity (HCP-PIMs), namely nitro-triptycene (TRIP-NO2), amino-triptycene (TRIP-NH2), sulfonated-triptycene (TRIP-SO3H) and hydrocarbon-triptycene (TRIP-HC), are employed for the adsorption of organic dyes from wastewater. The materials show the efficient removal of cationic (malachite green, MG) and anionic (methyl orange, MO) dyes. The adsorption parameters herein investigated include the initial pH, the adsorbate concentration and the contact time, with the aim to elucidate their effect on the adsorption process. Furthermore, the adsorption kinetic and isotherms are studied, and the findings suggest the results fit well with pseudo-second-order kinetics and Langmuir model. The reported maximum adsorption capacity is competitive for all the tested polymers. More specifically, TRIP-SO3H and TRIP-HC exhibit adsorptions of ~ 303 and ~ 270 mg g−1 for MG and MO, respectively. The selectivity toward cationic and anionic dyes is assessed by mixing the two dyes, and showing that TRIP-HC completely removes both species, whereas TRIP-NO2, TRIP-NH2 and TRIP-SO3H show an enhanced selectivity toward the cationic MG, compared to the anionic MO. The effect of the type of water is assessed by performing ultrasonic-assisted adsorption experiments, using TRIP-SO3H and TRIP-HC in the presence of either tap or seawater. The presence of competing ions and their concentrations is evaluated by ICP-MS. Our study shows that tap water does not have a detrimental effect on the adsorption of both polymers, whereas, in the presence of seawater, the performance of TRIP-HC toward MO proved to be more stable than MG with TRIP-SO3H, which is probably due to a larger concentration of competing ions. Comparison between ultrasonic-assisted and magnetic stirring adsorption demonstrates that the former exhibits a greater efficiency. This seems due to a more rapid mass transfer, driven by the formation of high velocity micro-jets, acoustic microstreaming and shock waves, at the polymer surface. Reusability studies show a good stability up to five adsorption–desorption cycles

Novel monomers for polymers of intrinsic microporosity (PIMs)

The research described in this thesis is directed towards the synthesis of novel monomers for preparing Polymers of Intrinsic Microporosity (PIMs). Each new monomer contains two catechol units fused via a spiro-centre, which adds a necessary site of contortion, and all are compatible with an efficient polymerisation reaction with 2,3,5,6-tetrafluoroterephthalonitrile. It was anticipated that the resulting PIMs would possess enhanced properties (e.g. microporosity, solubility gas permeability etc.) due to the polar and polarisable substituents that these novel monomers contribute to the polymer structure. This first part of this work describes the synthesis of two families of monomers. The first is based on the spiro-bisindane structural unit in which the spiro centre is shared by two fused five-membered rings, similar to the commercially available 4,4',5,5'-tetrahydroxy-3,3,3',3'-tetramethyl-l,r-spirobisindane, which was found to provide highly microporous polymers in previous work. Various groups (e.g. ketone, phenyl, fluorene) were introduced in place of the four methyl substituents. The second family of monomers is based upon l,l'-spiro-bis(1,2,4,5-tetrahydro-6,7-dihydroxynaphthalene) in which the spiro-centre fuses two six-membered rings. Similar substituents were introduced in order to make a direct comparison of properties to those of the polymers derived from the spirobisindane family. Additionally, the concept of adding 'sacrificial' thioketal groups to the 4,4',5,5'-tetrahydroxy-3,3'-keto-1,1'-spirobisindane monomer was investigated, with the aim of temporarily increasing the solubility and processability of the poorly soluble ketone-containing PIM. The last part of the work is concerned with the results of the polymerisation reactions of these novel monomers with 2,3,5,6-tetrafluoroterephthalonitrile, followed by the characterization of the resulting polymers. In particular, the important physical properties of the polymers were assessed such as solubility, molecular mass (by Gel Permeation Chromatography - GPC), microporosity (using nitrogen adsorption), and thermal stability (by Thermo-Gravimetric Analysis - TGA)

Polymers of Intrinsic Microporosity in the Design of Electrochemical Multi-Component and Multi-Phase Interfaces

Polymers of Intrinsic Microporosity (or PIMs) provide porous materials due to their highly contorted and rigid macromolecu-lar structures, which prevent space-efficient packing. PIMs are readily dissolved in solvents and can be cast into robust mi-croporous coatings and membranes. With a typical micropore size range of around 1 nm and a typical surface area of 700-1000 m2g-1, PIMs offer channels for ion/molecular transport and pores for gaseous species, solids, and liquids to coexist. Electrode surfaces are readily modified with coatings or composite films to provide interfaces for solid|solid|liquid or sol-id|liquid|liquid or solid|liquid|gas multiphase electrode processes

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 macromolecu-lar structures, which prevent space-efficient packing. PIMs are readily dissolved in solvents and can be cast into robust mi-croporous coatings and membranes. With a typical micropore size range of around 1 nm and a typical surface area of 700-1000 m2g-1, PIMs offer channels for ion/molecular transport and pores for gaseous species, solids, and liquids to coexist. Electrode surfaces are readily modified with coatings or composite films to provide interfaces for solid|solid|liquid or sol-id|liquid|liquid or solid|liquid|gas multiphase electrode processes