One-Pot Synthesis of High-Capacity Sulfur Cathodes via In-Situ Polymerization of a Porous Imine-Based Polymer.

Lithium-ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur-based cathodes, offering a high theoretical capacity of 1675 mAh g-1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state-of-the-art sulfur-based electrodes do not reach the theoretical capacities, mainly because conventional electrode production relies on mixing of components into weakly coordinated slurries. Consequently, sulfur's mobility leads to battery degradation-an effect known as the "sulfur-shuttle". This study introduces a solution by developing a microporous, covalently-bonded, imine-based polymer network grown in situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li-ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1 C (1360 mAh g-1) to 3 C (807 mAh g-1). Demonstrating a high-performance, sustainable sulfur cathode produced via a simple one-pot process, our research underlines the potential of microporous polymers in addressing sulfur diffusion issues, paving the way for sulfur electrodes as viable alternatives to traditional metal-based cathodes.

A π-Conjugated, Covalent Phosphinine Framework.

Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si, and S have found their way into their building blocks so far. Here, the toolbox available to polymer and materials chemists is expanded by one additional nonmetal, phosphorus. Starting with a building block that contains a λ5 -phosphinine (C5 P) moiety, a number of polymerization protocols are evaluated, finally obtaining a π-conjugated, covalent phosphinine-based framework (CPF-1) through Suzuki-Miyaura coupling. CPF-1 is a weakly porous polymer glass (72.4 m2 g-1 BET at 77 K) with green fluorescence (λmax =546 nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co-catalyst at a rate of 33.3 µmol h-1 g-1 . These results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine-based frameworks show promising electronic and optical properties, which might spark future interest in their applications in light-emitting devices and heterogeneous catalysis.

Molecular Mobility and Gas Transport Properties of Mixed Matrix Membranes Based on PIM-1 and a Phosphinine Containing Covalent Organic Framework.

Polymers with intrinsic microporosity (PIMs) are gaining attention as gas separation membranes. Nevertheless, they face limitations due to their pronounced physical aging. In this study, a covalent organic framework containing λ5-phosphinine moieties, CPSF-EtO, was incorporated as a nanofiller (concentration range 0-10 wt %) into a PIM-1 matrix forming dense films with a thickness of ca. 100 µm. The aim of the investigation was to investigate possible enhancements of gas transport properties and mitigating effects on physical aging. The incorporation of the nanofiller occurred on an nanoaggregate level with domains up to 100 nm, as observed by T-SEM and confirmed by X-ray scattering. Moreover, the X-ray data show that the structure of the microporous network of the PIM-1 matrix is changed by the nanofiller. As molecular mobility is fundamental for gas transport as well as for physical aging, the study includes dielectric investigations of pure PIM-1 and PIM-1/CPSF-EtO mixed matrix membranes to establish a correlation between the molecular mobility and the gas transport properties. Using the time-lag method, the gas permeability and the permselectivity were determined for N2, O2, CH4, and CO2 for samples with variation in filler content. A significant increase in the permeability of CH4 and CO2 (50% increase compared to pure PIM-1) was observed for a concentration of 5 wt % of the nanofiller. Furthermore, the most pronounced change in the permselectivity was found for the gas pair CO2/N2 at a filler concentration of 7 wt %.

Direct growth of crystalline triazine-based graphdiyne using surface-assisted deprotection-polymerisation.

Graphdiyne polymers have interesting electronic properties due to their π-conjugated structure and modular composition. Most of the known synthetic pathways for graphdiyne polymers yield amorphous solids because the irreversible formation of carbon-carbon bonds proceeds under kinetic control and because of defects introduced by the inherent chemical lability of terminal alkyne bonds in the monomers. Here, we present a one-pot surface-assisted deprotection/polymerisation protocol for the synthesis of crystalline graphdiynes over a copper surface starting with stable trimethylsilylated alkyne monomers. In comparison to conventional polymerisation protocols, our method yields large-area crystalline thin graphdiyne films and, at the same time, minimises detrimental effects on the monomers like oxidation or cyclotrimerisation side reactions typically associated with terminal alkynes. A detailed study of the reaction mechanism reveals that the deprotection and polymerisation of the monomer is promoted by Cu(ii) oxide/hydroxide species on the as-received copper surface. These findings pave the way for the scalable synthesis of crystalline graphdiyne-based materials as cohesive thin films.

Enhancement of osteoblast cells osteogenic differentiation and bone regeneration by hydroxyapatite/phosphoester modified poly(amino acid).

Hydroxyapatite/poly(amino acid) (HA/PAA) has been used to treat a variety of long bone and vertebral bony defects, and a further biocompatibility improvement is a key for better application. Phosphoester (PE) contained materials are highly biocompatible but could hardly treat massive bone defects due to its fast-degradation-derived mechanical instability. To address the problems of the two materials, we have incorporated PE molecule into the main chain of PAA by chemical bonding. As a result, the compressive strength of HA/PAA with 1 wt% and 2.5 wt% PE maintained in the range of 80-150 MPa after soaking in PBS for 12 weeks, which could be attributed to the amplified hydrogen-bonding inside composites. Besides, the PE-containing HA/PAAs with increased hydrophilic function groups (O=P-O bonds and O=P-N), created a more favourable surface for cell adhesion. Meanwhile, compared with HA/PAA, the PE-containing HA/PAAs had a fast minerlization speed and promoted cell osteogenic differentiation. Furthermore, the in vivo study indicated that PE-containing HA/PAAs could facilitate bone formation (4 weeks), and form a complete bone bridging (12 weeks) in a rabbit cranial bone defect. In summary, the HA/PE-m-PAAs possessed good mechanical stability, improved cytocompatibility and osteoconductivity, so the composites have a great potential for massive bone defect treatment.

Facile preparation of highly hydrophilic, recyclable high-performance polyimide adsorbents for the removal of heavy metal ions.

To obtain high-performance adsorbents that combine excellent adsorption ability, thermal stability, service life and recycling ability, polyimide (PI)/silica powders were prepared via a facile one-pot coprecipitation process. A benzimidazole unit was introduced into the PI backbone as the adsorption site. The benzimidazole unit induced more hydroxyls onto the silica, which provided hydrophilic sites for access by heavy metal ions. By comprehensively analyzing the effect of hydrophilcity, agglomeration, silica polycondensation, specific surface area and PI crystallinity, 10% was demonstrated to be the most proper feed silica content. The equilibrium adsorption amount (Qe) for Cu(2+) of PI/silica adsorbents was 77 times higher than that of pure PI. Hydrogen chloride (HCl) was used as a desorbent for heavy metal ions and could be decomplexed with benzimidazole unit at around 300°C, which was lower than the glass transition temperature of PI. The complexation and decomplexation process of HCl made PI/silica adsorbents recyclable, and the adsorption ability remained steady for more than 50 recycling processes. As PI/silica adsorbents possess excellent thermal stability, chemical resistance and radiation resistance and hydrophilicity, they have potential as superior recyclable adsorbents for collecting heavy metal ions from waste water in extreme environments.

High-yield production of highly fluorinated graphene by direct heating fluorination of graphene-oxide.

By employing honeycomb GO with large surface area as the starting materials and using elemental fluorine, we developed a novel, straightforward topotactic route toward highly fluorinated graphene in really large quantities at low temperature. The value of F/C molar ratio approaches to 1.02. Few-layer fluorinated graphene sheets are obtained, among which the yield of monolayered FG sheet is about 10% and the number of layers is mainly in the range of 2-5. Variations in morphology and chemical structure of fluorinated graphene were explored, and some physical properties were reported.