Cataloged from PDF version of article.Salty water! Lithium salts (LiCl, LiNO3, and LiClO4) at very high concentrations in water form lyotropic liquid crystalline (LLC) mesophases with a nonionic surfactant (10-lauryl ether) and display high ionic conductivities (10−2–10−4 S cm−1) over a broad temperature range (−10 to 80 °C) with excellent behavior as gel electrolytes in electrochemical applications

The zinc nitrate salt acts as a solvent in the ZnX-C 12 EO 10 (ZnX is [Zn(H 2 O) 6 ](NO 3 ) 2 and C 12 EO 10 is C 12 H 25 -(OCH 2 CH 2 ) 10 OH) lyotropic liquid crystalline (LLC) mesophase with a drastic dropping on the melting point of ZnX. The salt-surfactant LLC mesophase is stable down to -52°C and undergoes a phase change into a solid mesostructured salt upon cooling below -52°C; no phase separation is observed down to -190°C. The ZnX-C 12 EO 10 mesophase displays a usual phase behavior with an increasing concentration of the solvent (ZnX) in the media with an order of bicontinuous cubic(V 1 )-2D hexagonal(H 1 ) -a mixture of 2D hexagonal and micelle cubic(H 1 þ I)-micelle cubic(I)-micelle(L 1 ) phases. The phase behaviors, specifically at low temperatures, and the first phase diagram of the ZnX-C 12 EO 10 system was investigated using polarized optical microscopy (POM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and Raman techniques and conductivity measurements.

Proton conducting gel electrolytes are very important components of clean energy devices. Phosphoric acid (PA, H(3)PO(4) · H2O) is one of the best proton conductors, but needs to be incorporated into some matrix for real device applications, such as into lyotropic liquid crystalline mesophases (LLCMs). Herein, we show that PA and nonionic surfactant (NS, C(12)H(25)(OCH(2)CH(2))(10)OH, C(12)E(10)) molecules self-assemble into PANS-LLCMs and display high proton conductivity. The content of the PANS-LLCM can be as high 75% H(3)PO(4) · H2O and 25% 10-lauryl ether (C(12)H(25)(OCH(2)CH(2))(10)OH, C(12)E(10)), and the mesophase follows the usual LLC trend, bicontinuous cubic (V1)-normal hexagonal (H1)-micelle cubic (I1), by increasing the PA concentration in the media. The PANS-LLCMs are stable under ambient conditions, as well as at high (up to 130 °C) and low (-100 °C) temperatures with a high proton conductivity, in the range of 10(-2) to 10(-6) S/cm. The mesophase becomes a mesostructured solid with decent proton conductivity below -100 °C. The mesophase can be used in many applications as a proton-conducting media as well as a phosphate source for the synthesis of various metal phosphates. As an application, we demonstrate a graphene-based optical modulator using supercapacitor structure formed by graphene electrodes and a PANS electrolyte. A PANS-LLC electrolyte-based supercapacitor enables efficient optical modulation of graphene electrodes over a range of wavelengths, from 500 nm to 2 μm, under ambient conditions.

Uniform and homogeneous coating of mesoporous materials with an active (catalytically, photonic, electrical) nanostructure can be very useful for a number of applications. Understanding chemical reactions in a confined space is important in order to design new advanced materials. In this work, we demonstrate that an extensive amount (as high as 53 mol percent) of transition metal salts can be confined between silica walls and two surfactant domains (cetyltrimethylammonium bromide, CTAB, and lauryl ether, C 12 H 25 (OCH 2 CH 2 ) 10 OH, C 12 EO 10 ) as molten salts and then converted into sponge-like mesoporous silicaÀmetal oxides by thermal annealing. This investigation has been carried out using two different salts, namely, zinc nitrate hexahydrate, [Zn(H 2 O) 6 ](NO 3 ) 2 , and cadmium nitrate tetrahydrate, [Cd(H 2 O) 4 ](NO 3 ) 2 , in a broad range of salt concentrations. The ZnO (or CdO) layers are as thin as about ∼1.6 nm and are homogenously coated as crystalline nano-islands over the silica pore walls.

It is known that alkali, transition metal and lanthanide salts can form lyotropic liquid crystalline (LLC) mesophases with non-ionic surfactants (such as CiH2i+1(OCH2CH2)jOH, denoted as CiEj). Here we combine several salt systems and show that the percent deliquescence relative humidity (%DRH) value of a salt is the determining parameter in the formation and stability of the mesophases and that the other parameters are secondary and less significant. Accordingly, salts can be divided into 3 categories: Type I salts (such as LiCl, LiBr, LiI, LiNO3, LiClO4, CaCl2, Ca(NO3)2, MgCl2, and some transition metal nitrates) have low %DRH and form stable salt-surfactant LLC mesophases in the presence of a small amount of water, type II salts (such as some sodium and potassium salts) that are moderately hygroscopic form disordered stable mesophases, and type III salts that have high %DRH values, do not form stable LLC mesophases and leach out salt crystals. To illustrate this effect, a large group of salts from alkali and alkaline earth metals were investigated using XRD, POM, FTIR, and Raman techniques. Among the different salts investigated in this study, the LiX (where X is Cl(-), Br(-), I(-), NO3(-), and ClO4(-)) and CaX2 (X is Cl(-), and NO3(-)) salts were more prone to establish LLC mesophases because of their lower %DRH values. The phase behavior with respect to concentration, stability, and thermal behavior of Li(I) systems were investigated further. It is seen that the phase transitions among different anions in the Li(I) systems follow the Hofmeister series.