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丝光沸石纳米通道中受限水分子的¹H NMR研究。

(1)H NMR study of water molecules confined in nanochannels of mordenite.

作者信息

Panich A M, Sergeev N A, Paczwa M, Olszewski M

机构信息

Department of Physics, Ben-Gurion University of the Negev, P.O. Box 653, Be'er Sheva 8410501, Israel.

Institute of Physics, University of Szczecin, 70-451 Szczecin, Poland.

出版信息

Solid State Nucl Magn Reson. 2016 Jun-Jul;76-77:24-8. doi: 10.1016/j.ssnmr.2016.03.007. Epub 2016 Mar 23.

Abstract

Behavior of water molecules entrapped in nanochannels of zeolite mordenite has been investigated by (1)H NMR technique. The (1)H spectra and spin-lattice relaxation times in the laboratory and rotating frames, T1 and T1ρ, respectively, as well as the dipolar relaxation time T1D have been measured in the temperature range from 96 to 351K. Diffusion of water molecules along the channels was observed above ~200K. While in bulk liquid the dipolar ordered state of nuclear spins is not formed owing to complete motional average of dipolar interactions, we show that such a state is observed for mobile molecules confined in a restricted geometry. At temperatures below ~140K the relaxation was found to be mainly caused by interaction of (1)H nuclear spins with paramagnetic impurities. Complete lost of the fine structure of (1)H spectra above ~320 K is attributed to isotropic molecular reorientation or/and proton exchange. We show that the dipolar relaxation in mordenite is responsive to slow 180° reorientations of water molecules. The correlation times of nuclear and electron spin fluctuations were determined.

摘要

通过¹H NMR技术研究了被困在丝光沸石纳米通道中的水分子行为。在96至351K的温度范围内测量了¹H谱以及实验室坐标系和旋转坐标系中的自旋晶格弛豫时间T1和T1ρ,以及偶极弛豫时间T1D。在约200K以上观察到水分子沿通道的扩散。虽然在本体液体中,由于偶极相互作用的完全运动平均,核自旋的偶极有序态不会形成,但我们表明,对于限制在受限几何结构中的可移动分子,会观察到这样的状态。在低于约140K的温度下,发现弛豫主要由¹H核自旋与顺磁性杂质的相互作用引起。在约320K以上¹H谱精细结构的完全消失归因于各向同性分子重取向或/和质子交换。我们表明,丝光沸石中的偶极弛豫对水分子缓慢的180°重取向有响应。确定了核自旋和电子自旋涨落的相关时间。

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