Dual-Acid-Tailored Ionic Covalent Organic Frameworks for High-Temperature Proton Conduction under Anhydrous Conditions and the Practical Opportunities

IF 7 2区材料科学 Q2 CHEMISTRY, PHYSICAL Chemistry of Materials Pub Date : 2025-03-27 DOI:10.1021/acs.chemmater.5c00016

Vellaichamy Joseph, Keiichiro Maegawa, Mateusz Wlazło, Marek J. Potrzebowski, Krzysztof Łyczko, Atsushi Nagai

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Abstract

An organic salt (DMAP/Pa-SO₃H) composed of 2,5-diaminiobenzenesulfonic acid (Pa-SO₃H) and dimethylaminopyridine (DMAP) was demonstrated as a linker to construct ionic covalent organic frameworks (iCOFs). The iCOF denoted as TpDMAP/Pa-SO₃H was prepared by the condensation reaction of the triformylphloroglucinol (Tp) building block and DMAP/Pa-SO₃H and offers the potential to accommodate an external proton source (H₃PO₄; PA), enabling the immobilization of PA moieties within the pore structure through a strong ionic hydrogen bonding interaction evidenced by DFT calculations. Furthermore, H₃PO₄-doped iCOF denoted as PA@TpDMAP/Pa-SO₃H proclaimed the advantage of engineering at the linker position, which in turn promotes proton conductivity to 1.56 × 10^–2 S cm^–1 (increased 100-fold as related to PA@TpPa-SO₃H) at 140 °C under anhydrous conditions. Finally, we investigated the adaptability of a dual-acid system in sulfonated poly(ether ether ketone) (SPEEK) membranes, a common acid-modified polymeric material. PA-doped DMAP-modified SPEEK (PA@SPEEK/DMAP) evidenced a 100-fold appreciation of proton conductivity at 120 °C, as compared to bare SPEEK membranes under anhydrous conditions.

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无水条件下高温质子传导的双酸定制离子共价有机框架及其应用机遇

由2,5-二氨基苯磺酸（Pa-SO3H）和二甲氨基吡啶（DMAP）组成的有机盐（DMAP/Pa-SO3H）被证明是构建离子共价有机框架（iCOFs）的连接剂。TpDMAP/Pa-SO3H是由三甲酰间苯三酚（Tp）构筑块与DMAP/Pa-SO3H缩合反应制备的iCOF，具有容纳外部质子源(H3PO4；PA)，通过DFT计算证明了强离子氢键相互作用使PA部分在孔隙结构内固定。此外，h3po4掺杂的iCOF（表示为PA@TpDMAP/Pa-SO3H）表明在连接位置具有工程优势，从而在140°C无水条件下将质子电导率提高到1.56 × 10-2 S cm-1（与PA@TpPa-SO3H相比增加了100倍）。最后，我们研究了双酸体系在磺化聚醚醚酮（SPEEK）膜（一种常见的酸修饰聚合物材料）中的适应性。与无水条件下的裸SPEEK膜相比，pa掺杂DMAP修饰的SPEEK膜（PA@SPEEK/DMAP）在120°C时的质子电导率提高了100倍。

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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.