Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India.
J Phys Chem B. 2011 Aug 4;115(30):9395-400. doi: 10.1021/jp203821h. Epub 2011 Jul 11.
Temperature dependence study of the self-diffusion coefficient of Cs(+) ion in dibenzo-18-crown-6 (DB18C6) modified Nafion-117 (Cs-Naf-CR) was carried out in the temperature range of 50-65 °C. Temperature dependence of water diffusion in Cs-Naf-CR was also studied to understand the mechanism of cation and water transport in the membrane. Because of the very slow kinetics of isotopic exchange, self-diffusion measurement of Na(+) in Na-Naf-CR was carried out only at 60 °C. The result indicates that self-diffusion behavior is governed by the nature of the cation in which the crown ether was loaded in the membrane matrix. The activation energy of diffusion for Cs(+) ion and water in Cs-Naf-CR was found to be much higher than that in the pure Cs(+) form of Nafion (Cs-Naf). Water uptake of the membrane was also found to have reduced compared to Cs/Na-Naf. The results point to the binding of the ions by DB18C6 and the destruction of the water channels in the crown ether loaded membrane. The differential scanning calorimetry (DSC) data supports these observations.
在 50-65°C 的温度范围内,对负载二苯并-18-冠-6(DB18C6)的 Nafion-117(Cs-Naf-CR)中 Cs(+)离子自扩散系数的温度依赖性进行了研究。还研究了 Cs-Naf-CR 中水分扩散的温度依赖性,以了解膜中阳离子和水的传输机制。由于同位素交换的动力学非常缓慢,仅在 60°C 下对 Na-Naf-CR 中的 Na(+)进行了自扩散测量。结果表明,自扩散行为受负载在膜基质中的冠醚中阳离子的性质控制。Cs-Naf-CR 中 Cs(+)离子和水的扩散活化能明显高于纯 Nafion(Cs-Naf)中的 Cs(+)形式。与 Cs/Na-Naf 相比,膜的吸水率也有所降低。结果表明离子被 DB18C6 结合,并且负载冠醚的膜中的水通道被破坏。差示扫描量热法(DSC)数据支持这些观察结果。