Concentration-dependent supramolecular self-assembly of amphiphilic molecules in water furnishes a variety of nanostructured lyotropic liquid crystals (LLCs), which typically display high symmetry bicontinuous network and discontinuous micellar morphologies. Aqueous dispersions of soft spherical micelles derived from small molecule amphiphile hydration typically pack into exemplary body-centered cubic and closest-packed LLCs. However, investigations of hydrated mixtures of the ionic surfactant tetramethylammonium decanoate loaded with 40 wt % n-decane (TMADec-40) revealed the formation of a high symmetry bicontinuous double diamond LLC, as well as cubic C15 and hexagonal C14 Laves LLC phases that mirror the MgCu and MgZn intermetallic structure types, respectively. Detailed small-angle X-ray scattering analyses demonstrate that the complex C15 and C14 LLCs exhibit large unit cells, in which 12 or more ∼3-4 nm diameter micelles of multiple discrete sizes arrange into tetrahedral close packing arrangements with exceptional long-range translational order. The symmetry breaking that drives self-assembly into these low-symmetry LLC phases is rationalized in terms of a frustrated balance between maximizing counterion-mediated micellar cohesion within the ensemble of oil-swollen particles, while simultaneously optimizing local spherical particle symmetry to minimize molecular-level variations in surfactant solvation.
Network-phase lyotropic liquid crystals (LLCs) derived from the water-directed self-assembly of small molecule amphiphiles comprise a useful class of soft nanomaterials, with wide-ranging applications in structural biology and membrane science. However, few known surfactants enable access to these mesophases over wide temperature and amphiphile concentration phase windows. Recent studies have demonstrated that gemini ("twin tail") dicarboxylate surfactants, in which alkyl carboxylates are covalently linked near the headgroups by a hydrophobic bridge, exhibit increased propensities to form double gyroid network phase LLCs. We demonstrate herein that the lyotropic self-assembly behaviors of gemini dicarboxylates sensitively depend on the linker length, whereby odd-carbon linkers stabilize the double gyroid network LLC over unprecedented amphiphile concentration windows up to ∼45 wt % wide between T ≈ 22-80 °C. These self-assembly phenomena, which arise from the linker length-dependent preferred molecular conformations of these amphiphiles, will broaden the technological applications of these nanostructured LLCs.
A delicate balance of noncovalent interactions directs the hierarchical self-assembly of molecular amphiphiles into spherical micelles that pack into three-dimensional periodic arrays, which mimic intermetallic crystals. Herein, we report the discovery that adding water to a mixture of an ionic surfactant and n-decane induces aperiodic ordering of oil-swollen spherical micelles into previously unrecognized, aqueous lyotropic dodecagonal quasicrystals (DDQCs), which exhibit local 12-fold rotational symmetry and no long-range translational order. The emergence of these DDQCs at the nexus of dynamically arrested micellar glasses and a periodic Frank–Kasper (FK) σ phase approximant sensitively depends on the mixing order of molecular constituents in the assembly process and on sample thermal history. Addition of n-decane to mixtures of surfactant and water instead leads only to periodic FK A15 and σ approximants with no evidence for aperiodic order, while extended ambient temperature annealing of the DDQC also reveals its transformation into a σ phase. Thus, these lyotropic DDQCs are long-lived metastable morphologies, which nucleate and grow from a stochastic distribution of micelle sizes formed by abrupt segregation of varied amounts of oil into surfactant micelles on hydration. These findings indicate that molecular building block complexity is not a prerequisite for the formation of aperiodic supramolecular order, while also establishing the generic nature of quasicrystalline states across metal alloys and self-assembled micellar materials.
We report detailed small-angle X-ray scattering (SAXS) studies of the impact of variable n-decane loadings on the lyotropic liquid crystalline (LLC) phase behaviors of homologous bis(tetramethylammonium) gemini didecanoate surfactants TMA-7x, which derive from dimerizing decanoic acid through its α-carbon with hydrocarbyl linkers −(CH 2 ) x − where x = 3, 4, 5, and 6. TMA-7x amphiphiles with x = 3 or 5 exhibit a strong propensity to form normal double gyroid (G) LLC network mesophases over wide surfactant hydration ranges, as compared to homologues with x = 4 or 6. On swelling aqueous TMA-7x LLC mesophases with up to 35 wt % n-decane, we demonstrate that odd-carbon linked surfactants (x = 3 or 5) form G and normal double diamond (D) phases over wide water concentration windows with T = 22−100 °C. Complementary studies of decane-swollen TMA-7x (x = 4 or 6) aqueous LLCs instead demonstrate significantly diminished network phase stability, in favor of hexagonallypacked cylinder phases and a zoo of complex quasispherical micelle packings, which include micellar C14 and C15 Laves phases (P6 3 /mmc and Fd3(−)m symmetries, respectively) and high-symmetry hexagonally close packed (HCP) and body-centered cubic (BCC) arrangements. These rich phase behaviors are rationalized in terms of linker length parity-dependent surfactant conformations and the delicate free energy balance that guides the packing of these geometrically anisotropic amphiphiles by minimizing unfavorable water-hydrophobic contacts, maximizing ionic surfactant-headgroup counterion solvation with minimal local variations, and maximizing electrostatic cohesion within these supramolecular assemblies.
Carbon-based porous electrodes are of particular interest for electrochemical energy conversion devices, such as fuel cells and electrolyzers. These catalyst layer electrodes are formed by coating a thin liquid film on a substrate and then drying it to form the porous electrode. During the drying process, the liquid receding through the particle matrix leads to the development of stresses, which when large enough, cause the film to crack. In fuel cells, cracks in the catalyst layer (CL) negatively impact its electrochemical performance and membrane-electrode-assembly durability. Although mitigation of this physical phenomena is of significant importance, the interaction- and process-driven parameters that govern cracks – such as ink composition, mixing method, and coating techniques – are poorly understood. Herein, we investigate the effects of polymeric additives on platinum on carbon (Pt/C) cathode CL crack formation. Small quantities of polymeric additives – which account for < 1% of total ink composition – are inserted to water- and n-propanol-predominant formulations prior to the final mixing stage. Rod-coated samples with estimated Pt loadings of 0.280 mg/cm2 show no signs of surface cracks for water-rich CLs, whereas the area occupied by these defects is reduced up to 55% in alcohol-rich gas diffusion electrodes (GDEs). In-situ electrochemical performance and durability tests are incorporated to assess the impact of these polymeric additives in nearly crack-free coatings against their cracked, nonadditive GDE counterparts. Figure 1
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