Grafting of Poly(vinyl phosphonic acid) to MOF Surfaces to Achieve Proton Conducting Hybrid Materials,ACS Applied Polymer Materials

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Grafting of Poly(vinyl phosphonic acid) to MOF Surfaces to Achieve Proton Conducting Hybrid Materials
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2024-06-20 , DOI: 10.1021/acsapm.4c00821
Nilanjan Mukherjee ₁ , Olivia Basu ₁ , Subhabrata Mukhopadhyay ₁ , Tushar Jana ₁

Affiliation

In recent times, surface-modified metal organic frameworks (MOFs), obtained using different postsynthetic modifications (PSMs) on MOFs, are being explored frequently to develop hybrid materials for numerous applications. In continuation of our recent work on the grafting of polymer chains on the MOF surface to make hybrid materials (polymer-MOF conjugates) with enhanced physical properties, in this work, we grafted a proton conducting polymer, namely, poly(vinyl phosphonic acid) [PVPA] chains of various length and grafting density, on UiO-66 MOF, using surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization in order to develop an advanced class of proton conducting MOF-based hybrid materials with superior performance. Grafting of PVPA chains was confirmed by TGA, GPC, FT-IR, NMR, FESEM, TEM, EDX, and mapping studies. The stability of the freshly synthesized hybrid material under various harsh environments was further analyzed. Pendent phosphonic acid groups of the PVPA chains grafted on the MOF surface create strong H-bonding, acid–base, ionic, and noncovalent interactions with the neighboring PGMs and water molecules, which are responsible for displaying high stability, water sorption ability, and high proton conductivity of 1.26 × 10^–2 S cm^–1 at 80 °C for the PGM-L3 sample under 98% relative humidity and 9.8 × 10^–3 S cm^–1 at 60 °C for the PGM-H1 sample under 75% relative humidity, which are among the highest values reported so far for MOF-based systems.

中文翻译：

将聚（乙烯基膦酸）接枝到 MOF 表面以实现质子传导杂化材料

近年来，人们经常探索通过对 MOF 进行不同的合成后修饰 (PSM) 获得的表面改性金属有机骨架 (MOF)，以开发适合多种应用的混合材料。继续我们最近在 MOF 表面接枝聚合物链以制造具有增强物理性能的杂化材料（聚合物-MOF 缀合物）的工作，在这项工作中，我们接枝了一种质子传导聚合物，即聚（乙烯基膦酸）使用表面引发的可逆加成-断裂链转移 (SI-RAFT) 聚合，在 UiO-66 MOF 上形成不同长度和接枝密度的 [PVPA] 链，以开发一种先进的质子传导 MOF 基杂化材料，具有优异的性能表现。 PVPA 链的接枝通过 TGA、GPC、FT-IR、NMR、FESEM、TEM、EDX 和绘图研究得到证实。进一步分析了新合成的杂化材料在各种恶劣环境下的稳定性。接枝在 MOF 表面的 PVPA 链的侧链膦酸基团与邻近的 PGM 和水分子产生强烈的氢键、酸碱、离子和非共价相互作用，从而表现出高稳定性、吸水能力和高吸附能力。 PGM-L3 样品在 80 °C、98% 相对湿度和 9.8 × 10 ^–3 S cm 下的质子电导率为 1.26 × 10 ^–2 S cm ^–1 ^–1 在 60 °C 下，PGM-H1 样品在 75% 相对湿度下，这是迄今为止报道的基于 MOF 的系统的最高值之一。

更新日期：2024-06-20

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