Nanometrically Confined Water Molecules in 2D Polyoxometalate-Based Metal–Organic Frameworks Enhancing Proton Conductivity

IF 9.6 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Materials Letters Pub Date : 2025-03-20 DOI:10.1021/acsmaterialslett.5c0033310.1021/acsmaterialslett.5c00333

Yu-Ming Cui, Bao-Yue Zhang, Jing Sun*, Xingqi Han*, Xue-Song Wu* and Zhong-Min Su,

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Abstract

Confining water molecules within sub1 nm channels is recognized as an effective strategy for improving proton conductivity. Utilizing a hydrothermal synthesis approach, two new two-dimensional (2D) polyoxometalate-based metal–organic frameworks (POMOFs) were successfully synthesized, named [Ni(Bip)₂(H₂O)₂(γ-Mo₈O₂₆)]·3H₂O (CUST-862) and [Co₂(Bip)₂(H₂O)₄(γ-Mo₈O₂₆)]·2H₂O (CUST-863). Thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD) results demonstrated that both compounds exhibit excellent water stability and thermal stability. Alternating current (AC) impedance spectroscopy revealed that CUST-862 achieved a maximum proton conductivity of 1.97 × 10^–3 S cm^–1, which is an order of magnitude higher than that of CUST-863 under conditions of 90 °C and 98% relative humidity (RH). The space confined effect of sub-1-nm channels acting on free molecules in CUST-862 effectively enhances the proton conductivity. The results obtained from attenuated total reflection infrared (ATR-IR) and water vapor adsorption–desorption tests offered a comprehensive explanation for the confinement effect. This research gives a novel approach for enhancing proton conductivities in POMs-based materials.

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二维多金属氧酸盐基金属有机框架中的纳米限制水分子增强质子电导率

将水分子限制在小于1nm的通道内被认为是提高质子电导率的有效策略。利用水热合成方法，成功合成了两个新的二维（2D）多金属氧酸盐基金属有机骨架（POMOFs），分别命名为[Ni(Bip)2(H2O)2(γ-Mo8O26)]·3H2O （CUST-862）和[Co2(Bip)2(H2O)4(γ-Mo8O26)]·2H2O （CUST-863）。热重分析（TGA）和粉末x射线衍射（PXRD）结果表明，两种化合物均具有优异的水稳定性和热稳定性。交流阻抗谱显示，在90℃和98%相对湿度条件下，CUST-862的最大质子电导率为1.97 × 10-3 S cm-1，比CUST-863高出一个数量级。在CUST-862中，亚1nm通道作用于自由分子的空间限制效应有效地提高了质子的电导率。衰减全反射红外（ATR-IR）和水蒸气吸附-解吸试验的结果为约束效应提供了全面的解释。本研究为提高聚甲醛基材料的质子电导率提供了一种新的途径。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

期刊介绍： ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.