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多核脉冲场梯度自旋回波核磁共振(Multinuclear PFGSTE NMR)对控制碱金属亚硝酸盐溶液中扩散的钾、钠、锂和氢的比活化能的描述。

Multinuclear PFGSTE NMR description of K, Na, Li, and H specific activation energies governing diffusion in alkali nitrite solutions.

作者信息

Graham Trent R, Kennedy Ashley R, Felsted Robert G, Colina-Ruiz Roberto A, Nienhuis Emily T, Reynolds Jacob G, Pearce Carolyn I

机构信息

Pacific Northwest National Laboratory, Richland, WA 99354, USA.

Pacific Northwest National Laboratory, Richland, WA 99354, USA; Savannah River National Laboratory, Aiken, SC 29808, USA.

出版信息

J Magn Reson. 2024 Jul;364:107707. doi: 10.1016/j.jmr.2024.107707. Epub 2024 Jun 3.

Abstract

While pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has found widespread use in the quantification of self-diffusivity for many NMR-active nuclei, extending this technique to uncommon nuclei with unfavorable NMR properties remains an active area of research. Potassium-39 (K) is an archetypical NMR nucleus exhibiting an unfavorable gyromagnetic ratio combined with a very low Larmor frequency. Despite these unfavorable properties, this work demonstrates that K PFGSTE NMR experiments are possible in aqueous solutions of concentrated potassium nitrite. Analysis of the results indicates that K NMR diffusometry is feasible when the nuclei exhibit spin-lattice and spin-spin relaxation coefficients on the order of 60-100 ms and 50-100 ms, respectively. The diffusivity of K followed Arrhenius behavior, and comparative Na, Li, and H PFGSTE NMR studies of equimolal sodium nitrite and lithium nitrite solutions led to correlations between the enthalpy of hydration with the activation energy governing self-diffusion of the cations and also of water. Realizing the feasibility of K PFGSTE NMR spectroscopy has a widespread impact across energy sciences because potassium is a common alkali element in energy storage materials and other applications.

摘要

虽然脉冲场梯度刺激回波核磁共振(PFGSTE NMR)光谱法已在许多具有NMR活性的核的自扩散定量分析中得到广泛应用,但将该技术扩展到具有不利NMR性质的不常见核仍属活跃的研究领域。钾-39(K)是一种典型的NMR核,其旋磁比不利,拉莫尔频率极低。尽管有这些不利性质,但这项工作表明在浓亚硝酸钾水溶液中进行K PFGSTE NMR实验是可行的。结果分析表明,当核的自旋晶格弛豫系数和自旋-自旋弛豫系数分别在60 - 100毫秒和50 - 100毫秒量级时,K NMR扩散测量是可行的。K的扩散率遵循阿仑尼乌斯行为,并且对亚硝酸钠和亚硝酸锂等摩尔溶液进行的Na、Li和H PFGSTE NMR对比研究得出了水合焓与控制阳离子以及水自扩散的活化能之间的相关性。认识到K PFGSTE NMR光谱法的可行性对能源科学有着广泛影响,因为钾是储能材料及其他应用中的常见碱金属元素。

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