Hydrophilic vs Hydrophobic: Exploring Facet-Dependent Proton Transport Channels in Single Crystal of Ring-Shaped Trimeric Isopolytungstate

IF 7 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2024-09-06 DOI:10.1021/acs.chemmater.4c0181810.1021/acs.chemmater.4c01818

Mengnan Yang, Lijuan Xiong, Shiyan Ji, Yao Zhang, Weixia Shi, Huafeng Li, Pengtao Ma, Jingping Wang* and Jingyang Niu*,

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Abstract

Research on the facet-dependent anisotropic proton conduction of single crystals is advantageous to visualize the molecular level mechanism of polyoxometalate (POM)-based crystalline proton-conducting materials. Herein, we constructed a novel ring-shaped trimeric isopolytungstate {(RuW₁₁O₃₇)O}₃^18– (1a) with an inner hydrophobic space and an outer hydrophilic surface. After assembly through the hydrated cation linkers, polyanion 1a rings formed the single-crystal Rb₁₁Na₆H·1a·36H₂O (1) with (01̅0), (101), and (1̅11) faces, which have different sizes and types (hydrophilic-Grotthuss-type and/or hydrophobic-Vehicle-type) of proton transport channels. Accordingly, proton conductivity (σ) of single-crystal 1 can reach 3.84 × 10^–2 S cm^–1 along the direction perpendicular to the (01̅0) face at 358 K under 85% relative humidity (RH), which is equivalent to that of crystal pellet (2.09 × 10^–2 S cm^–1) and accompanied by the ratio of σ_(01̅0):σ₍₁₀₁₎:σ_(1̅11) = 121:5:1. It reveals a visible (01̅0) facet-dependent proton-conducting pathway in the large-sized hydrophilic pore channels through a water-induced hydrogen bond network under the Grotthuss hopping mechanism.

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亲水与疏水：探索环形三聚异多钨酸盐单晶中的面依赖性质子传输通道

研究单晶的面依赖性各向异性质子传导有利于直观地了解基于聚氧化金属（POM）的晶体质子传导材料的分子水平机理。在此，我们构建了一种新型环形三聚异钨酸盐{(RuW11O37)O}318-（1a），其内部为疏水空间，外部为亲水表面。通过水合阳离子连接体组装后，多阴离子 1a 环形成了具有 (01̅0)、(101) 和 (1̅11) 面的单晶 Rb11Na6H-1a-36H2O (1)，它们具有不同大小和类型（亲水-Grotthuss 型和/或疏水-车辆型）的质子传输通道。因此，在相对湿度（RH）为 85% 的条件下，358 K 时单晶 1 沿垂直于（01̅0）面的方向的质子传导率（σ）可达 3.84 × 10-2 S cm-1，与晶体颗粒（2.09 × 10-2 S cm-1）相当，且σ(01̅0):σ(101):σ(1̅11) = 121:5:1。它揭示了在 Grotthuss 跳变机制下，通过水诱导的氢键网络，在大尺寸亲水孔道中形成了一条可见的 (01̅0) 面依赖质子传导途径。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.