Ligand Valency Effects on the Alkaline Stability of Metallopolymer Anion-Exchange Membranes,Macromolecular Rapid Communications

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Ligand Valency Effects on the Alkaline Stability of Metallopolymer Anion-Exchange Membranes
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2021-06-25 , DOI: 10.1002/marc.202100238
Kanika Aggarwal ₁ , Saja Bsoul ₂ , Songlin Li ₂ , Dario R Dekel _{2,

3} , Charles E Diesendruck _{1,

3}

Affiliation

Long-term stability is a key requirement for anion-exchange membranes (AEMs) for alkaline fuel cells and electrolyzers that is yet to be fulfilled. Different cationic chemistries are being exploited to reach such a goal, and metallopolymers present the unique advantage of chemical stability towards strong nucleophiles as compared to organic cations. Yet, the few metallopolymers tested in strongly alkaline conditions or even in fuel cells still degrade. Therefore, fundamental studies can be advantageous in directing future developments towards this goal. Here, a systematic study of the effect of ligand valency is presented, using nickel-based metallopolymers on polynorbornene backbones, functionalized with multidentate pyridine ligands. Metallopolymers using a single ligand type as well as all the possible mixtures are prepared and their relative stability towards aggressive alkaline conditions compared. Metallopolymer in which nickel ions are hexacoordinated with two tridentate ligands demonstrates superior stability. More importantly, by comparing all the metallopolymers’ stability, the reason behind such relative stability provides design parameters for novel metallopolymer AEMs.

中文翻译：

配体价态对金属聚合物阴离子交换膜碱性稳定性的影响

长期稳定性是用于碱性燃料电池和电解槽的阴离子交换膜 (AEM) 的关键要求，但尚未满足。正在开发不同的阳离子化学来达到这样的目标，与有机阳离子相比，金属聚合物对强亲核试剂具有化学稳定性的独特优势。然而，在强碱性条件下或什至在燃料电池中测试的少数金属聚合物仍然会降解。因此，基础研究可以有利于指导未来的发展朝着这个目标发展。在这里，系统研究了配体化合价的影响，在聚降冰片烯骨架上使用镍基金属聚合物，用多齿吡啶配体功能化。制备了使用单一配体类型以及所有可能混合物的金属聚合物，并比较了它们对侵蚀性碱性条件的相对稳定性。镍离子与两个三齿配体六配位的金属聚合物显示出优异的稳定性。更重要的是，通过比较所有金属聚合物的稳定性，这种相对稳定性背后的原因为新型金属聚合物 AEM 提供了设计参数。

更新日期：2021-08-20

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