Effect of introducing a cyclobutylmethyl group into an onium cation on the thermodynamic properties of ionic clathrate hydrates
Effect of introducing a cyclobutylmethyl group into an onium cation on the thermodynamic properties of ionic clathrate hydrates
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鎓阳离子中引入环丁基甲基对离子笼形水合物热力学性质的影响
DOI：
10.1039/d2nj04361k
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发表时间：
2023
影响因子：
3.3
通讯作者：
Hirai Takayuki
中科院分区：
文献类型：
--
作者：
Azuma Sakura;Shimada Jin;Tsunashima Katsuhiko;Sugahara Takeshi;Hirai Takayuki
离子笼状水合物(ICHs)已被应用于储热材料，可作为一种特殊的热能资源加以利用。在本研究中，我们开发了一种新型的ICH，其中包括三正丁基(环丁基甲基)溴化膦(P444(1C4)-BR)作为一个前所未有的客体物种。在摩尔分数为279.5±0.0008时，P444(1C4)-BrICH的最高平衡温度为279.5±0.1K，最高离解热为202±2Jg−1。P444(1C4)-BrICH的最高平衡温度略低于四正丁基溴化膦(P4444-BrICH)。在相同的最高平衡温度下，P444(1C4)-BrICH的离解热大于其他ICH。环状碳氢化合物与正、支链、饱和碳氢链和不饱和碳氢链一起，可以作为调节ICH平衡温度的选择之一。
Ionic clathrate hydrates (ICHs) have been applied to thermal storage materials, which can be utilized as unusual thermal energy sources. In the present study, we developed a novel ICH including tri-n-butyl(cyclobutylmethyl)phosphonium bromide (P444(1c4)-Br) as an unprecedented guest species. The highest equilibrium temperature and the dissociation enthalpy of P444(1c4)-Br ICH were 279.5 ± 0.1 K and 202 ± 2 J g−1, respectively, at the mole fraction of 0.0255 ± 0.0008. The highest equilibrium temperature of P444(1c4)-Br ICH was slightly lower than that of the tetra-n-butylphosphonium bromide (P4444-Br) ICH. The dissociation enthalpy of P444(1c4)-Br ICH was larger than that of other ICHs with similar highest equilibrium temperatures. Cyclic hydrocarbon groups, together with normal, branched, saturated, and unsaturated hydrocarbon chains, can be one of the options for tuning the equilibrium temperature of ICHs.