No abstract

The alkaline stability of N‐heterocyclic ammonium (NHA) groups is a critical topic in anion‐exchange membranes (AEMs) and AEM fuel cells (AEMFCs). Here, we report a systematic study on the alkaline stability of 24 representative NHA groups at different hydration numbers (λ) at 80 °C. The results elucidate that γ‐substituted NHAs containing electron‐donating groups display superior alkaline stability, while electron‐withdrawing substituents are detrimental to durable NHAs. Density‐functional‐theory calculations and experimental results suggest that nucleophilic substitution is the dominant degradation pathway in NHAs, while Hofmann elimination is the primary degradation pathway for NHA‐based AEMs. Different degradation pathways determine the alkaline stability of NHAs or NHA‐based AEMs. AEMFC durability (from 1 A cm−2 to 3 A cm−2) suggests that NHA‐based AEMs are mainly subjected to Hofmann elimination under 1 A cm−2 current density for 1000 h, providing insights into the relationship between current density, λ value, and durability of NHA‐based AEMs.

We systematically investigated the effect of incorporating a sterically hindered pyridyl group into a sulfophenylated polyphenylene to control the polymer's physicochemical properties through acid−base interactions. Homopolymers with similar molecular weights and comparable structures that vary by only one atom (N− vs C−) per repeat unit along the polymer chain were prepared. Compared to a non-pyridyl reference membrane, incorporation of a pyridyl group improves the oxidative stability against free radicals, increases the elongation at break to 55% (from 37%), and enhances the thermal stability to 326 °C (from 246 °C). In an accelerated fuel cell degradation test, polymeric membranes containing the sterically encumbered pyridyl unit exhibited exceptional stability (0.16 mV h −1 degradation rate over 1000 h) and retained ∼80% of their peak power density over this time.

A 24-fold reduction in reaction time is achieved in the preparation of sulfonated poly(polyphenylene)s using microwave synthesis.

This article describes a novel supramolecular assembly-mediated strategy for the organization of Au nanoparticles (NPs) with different shapes (e.g., spheres, rods, and cubes) into large-area, free-standing 2D and 3D superlattices. This robust approach involves two major steps: (i) the organization of polymer-tethered NPs within the assemblies of supramolecular comblike block copolymers (CBCPs), and (ii) the disassembly of the assembled CBCP structures to produce free-standing NP superlattices. It is demonstrated that the crystal structures and lattice constants of the superlattices can be readily tailored by varying the molecular weight of tethered polymers, the volume fraction of NPs, and the matrix of CBCPs. This template-free approach may open a new avenue for the assembly of NPs into 2D and 3D structures with a wide range of potential applications.