天然沸石中离子交换平衡的离子特异性研究

Ion Specificity During Ion Exchange Equilibrium in Natural Clinoptilolite

沸石在改良土壤和保护环境等方面有着广泛的应用,研究沸石离子交换中的特异性效应对更好地利用沸石有着重要意义.碱金属离子在天然斜发沸石中的交换平衡时的最大吸附量存在着明显的特异性效应;对于同价的碱金属离子,其交换吸附能力差异随着离子浓度的降低而增大.这种实验现象不能用库仑力、离子体积、水合作用、色散力、经典诱导力以及表面络合等相关理论进行完整解释.分析发现,根本原因来自离子因量子涨落而产生的极化与沸石颗粒表面电荷产生的强电场之间的相互作用,这种相互作用导致了离子间偶极矩差异随着表面电位的升高而增大,进而使离子-表面吸附能差异增大,并出现不同的交换吸附能力.由于沸石表面电荷密度较高,离子体积效应对其在双电层中的分布也起着比较重要的作用,导致碱金属离子在沸石表面的交换平衡结果在高表面电位(绝对值大于0.2 V)下才表现出较大选择性,与低电荷密度表面上的交换平衡结果存在一定差异.

Zeolites have been widely applied in soil improvement and environment protection. The study on ion specificity during ion exchange equilibrium is of important significance for better use of zeolites. The maximum adsorption capacities of alkali ions during ion exchange equilibrium in the clinoptilolite showed obvious specificity. For alkali metal ions with equivalent valence,the differences in adsorption capacity increased with the decrease of ionic concentration. These results cannot be well explained by the classical theories including coulomb force,ionic size,hydration,dispersion force,classic induction force and surface complexation. We found that the coupling of polarization effects resulted from the quantum fluctuation of diverse alkali metal ions and electric field near the zeolite surface should be the primary reason for specific ion effect during ion exchange in zeolite. The result of this coupling effect was that the difference in the ion dipole moment increased with the increase of surface potential,which further expanded the difference in the adsorption ability between zeolite surface and ions,resulting in different ion exchange adsorption ability at the solid / liquid interface.Due to the high surface charge density of zeolite,ionic size also played an important role in the distribution of ions in the double diffuse layer,which led to an interesting result that distinct differences in exchange adsorption ability of various alkali metal ions were only detected at high surface potential( the absolute value was greater than 0. 2 V),which was different from the ion exchange equilibrium result on the surface with low charge density.