Shuai Tan

Anisotropic assembly of a side chain liquid crystal polymer containing sulfoalkoxy groups for anhydrous proton conduction

A side chain liquid crystal polymer containing pendant sulfonic acid groups has been synthesized by post-polymerization functionalization of a brominated mesogenic precursor. A macroscopic alignment was achieved by mechanical shearing of the liquid crystal polymer in the smectic phase. The uniaxial layered assembly exhibited anisotropic proton conductivities under anhydrous conditions and has potential applications in medium temperature fuel cells.

Anhydrous proton conduction in liquid crystals containing benzimidazole moieties

A homologous series of biphenyl benzoate-based compounds with an alkthio chain bearing a benzimidazole moiety at the termini was synthesized by a nucleophilic substitution reaction. The compounds exhibited smectic A and nematic phases over a temperature range of 173–116 °C during the cooling process. A partially interdigitated bilayer order developed in the smectic assemblies and hydrogen-bonding between the benzimidazole moieties extended along the plane parallel to the smectic layer. Electrochemical characterization revealed that the liquid crystal phases favoured anhydrous proton conduction in the benzimidazole compounds and a proton conductivity of 4.4 × 10−5 S cm−1 was achieved at 173 °C. The temperature dependence of the proton conductivities approximately followed the Arrhenius law and the proton conduction in the benzimidazole liquid crystals was assumed to be dominated by the proton hopping mechanism.

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.