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介电谱法研究分子筛中的水动力学

Dynamics of water in molecular sieves by dielectric spectroscopy.

作者信息

Jansson H, Swenson J

机构信息

Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden.

出版信息

Eur Phys J E Soft Matter. 2003 Nov;12 Suppl 1:S51-4. doi: 10.1140/epjed/e2003-01-013-5. Epub 2003 Nov 5.

Abstract

We present recent dielectric data on the dynamics of water confined in molecular sieves with pore sizes 5 and 10 A. The dielectric measurements in the frequency and temperature ranges 10(-2)-10(6) Hz and 120-300 K show three relaxation processes for both samples. In the case of the 10 A pore the slowest process shows an Arrhenius temperature dependence at low temperatures (<220 K), while at high temperatures the relaxation appears to follow a more Vogel-Fulcher-Tammann (VFT) like behaviour. The relaxation time for this process is 100 s at about 170 K. The second slowest process is at low temperatures very similar to the main process of (bulk-like) water in a fully hydrated clay, but also this process seems to exhibit some kind of dynamical transition, in this case at T approximately 185 K. All the three processes in the 5 A pore exhibit Arrhenius temperature dependence, and two of them are considerably slower than the main relaxation in the hydrated clay. Thus, dynamics of bulk-like water is only observed in the 10 A molecular sieves, and most of the water molecules in both 5 and 10 A pores have considerably slower dielectric relaxation than has been observed for water confined in clay, most likely due to strong interactions with the considerably more hydrophilic inner surfaces of molecular sieves.

摘要

我们展示了近期关于孔径为5埃和10埃的分子筛中受限水动力学的介电数据。在10⁻² - 10⁶赫兹频率范围和120 - 300开尔文温度范围内的介电测量表明,两个样品都有三个弛豫过程。对于孔径为10埃的情况,最慢的过程在低温(<220开尔文)下呈现阿仑尼乌斯温度依赖性,而在高温下弛豫似乎遵循更类似沃格尔 - 富尔彻 - 塔曼(VFT)的行为。该过程的弛豫时间在约170开尔文时为100秒。第二慢的过程在低温下与完全水合粘土中(类似本体)水的主要过程非常相似,但这个过程似乎也表现出某种动力学转变,在这种情况下转变温度约为185开尔文。孔径为5埃的所有三个过程都呈现阿仑尼乌斯温度依赖性,其中两个过程比水合粘土中的主要弛豫慢得多。因此,仅在孔径为10埃的分子筛中观察到类似本体水的动力学,并且孔径为5埃和10埃的分子筛中大多数水分子的介电弛豫比在粘土中受限水的弛豫慢得多,这很可能是由于与分子筛更亲水的内表面的强相互作用。

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