Olutaş Elif B, Balcı Fadime M, Dag Ömer
Bilkent University , Department of Chemistry, 06800 Ankara, Turkey.
Department of Chemistry, Abant İzzet Baysal University , 14280 Bolu, Turkey.
Langmuir. 2015 Sep 22;31(37):10265-71. doi: 10.1021/acs.langmuir.5b02225. Epub 2015 Sep 10.
Lyotropic liquid-crystalline (LLC) materials are important in designing porous materials, and acids are as important in chemical synthesis. Combining these two important concepts will be highly beneficial to chemistry and material science. In this work, we show that a strong acid can be used as a solvent for the assembly of nonionic surfactants into various mesophases. Sulfuric acid (SA), 10-lauryl ether (C12E10), and a small amount of water form bicontinuous cubic (V1), 2D-hexagonal (H1), and micelle cubic (I1) mesophases with increasing SA/C12E10 mole ratio. A mixture of SA and C12E10 is fluidic but transforms to a highly ordered LLC mesophase by absorbing ambient water. The LLC mesophase displays high proton conductivity (1.5 to 19.0 mS/cm at room temperature) that increases with an increasing SA content up to 11 SA/C12E10 mole ratio, where the absorbed water is constant with respect to the SA amount but gradually increases from a 2.3 to 4.3 H2O/C12E10 mole ratio with increasing SA/C12E10 from 2 to 11, respectively. The mixture of SA and C12E10 slowly undergoes carbonization to produce carbon quantum dots (c-dots). The carbonization process can be controlled by simply controlling the water content of the media, and it can be almost halted by leaving the samples under ambient conditions, where the mixture slowly absorbs water to form photoluminescent c-dot-embedded mesophases. Over time the c-dots grow in size and increase in number, and the photoluminescence frequency gradually shifts to a lower frequency. The SA/C12E10 mesophase can also be used as a template to produce highly proton conducting mesostructured silica films and monoliths, as high as 19.3 mS/cm under ambient conditions. Aging the silica samples enhances the conductivity that can be even larger than for the LLC mesophase with the same amount of SA. The presence of silica has a positive effect on the proton conductivity of SA/C12E10 systems.
溶致液晶(LLC)材料在多孔材料设计中很重要,而酸在化学合成中同样重要。将这两个重要概念结合起来对化学和材料科学将非常有益。在这项工作中,我们表明强酸可作为溶剂,用于将非离子表面活性剂组装成各种中间相。硫酸(SA)、十二烷基醚(C12E10)和少量水随着SA/C12E10摩尔比的增加形成双连续立方相(V1)、二维六方相(H1)和胶束立方相(I1)中间相。SA和C12E10的混合物是流体状的,但通过吸收环境中的水转变为高度有序的LLC中间相。该LLC中间相显示出高质子传导率(室温下为1.5至19.0 mS/cm),随着SA含量增加至11 SA/C12E10摩尔比而增加,此时吸收的水相对于SA量保持恒定,但随着SA/C12E10从2增加到11,水的摩尔比从2.3逐渐增加到4.3 H2O/C12E10。SA和C12E10的混合物会缓慢碳化以产生碳量子点(c-点)。碳化过程可通过简单控制介质的含水量来控制,将样品置于环境条件下,混合物会缓慢吸收水形成嵌入光致发光c-点的中间相,碳化过程几乎可以停止。随着时间推移,c-点尺寸增大且数量增加,光致发光频率逐渐向低频移动。SA/C12E10中间相还可作为模板来制备高质子传导的介孔结构二氧化硅薄膜和整体材料,在环境条件下高达19.3 mS/cm。对二氧化硅样品进行老化可提高传导率,甚至可能高于相同SA含量的LLC中间相。二氧化硅的存在对SA/C12E10体系的质子传导率有积极影响。