Vapor-phase zeolitic imidazolate framework-8 growth on fibrous polymer substrates

Rachel A. Nye, Nicholas M. Carroll, Sarah E. Morgan, Gregory N. Parsons
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Abstract

The use of metal-organic frameworks (MOFs) in practical applications is often hindered by synthesis related challenges. Conventional solution-based approaches rely on hazardous solvents and often form powders that are difficult to integrate into practical devices. On the other hand, vapor-phase approaches generally result in MOF films on silicon substrates that make it difficult to characterize the MOF surface area, which is an important quality indicator. We address these challenges by introducing a solvent-free synthesis method to form MOF–fiber composites, which can be more easily integrated into devices. Additionally, these vapor-phase-formed MOF–fiber composites are compatible with Brunauer–Emmett–Teller surface area analysis to characterize MOF quality. Atomic layer deposition is used to form a ZnO film on polypropylene, polyester, and nylon fibrous substrates, which is subsequently converted to zeolitic imidazolate framework-8 (ZIF-8) using 2-methylimidazole vapor. We describe the effects of the ZnO film thickness and MOF conversion conditions on MOF crystallinity and surface area. We report a ZIF-8 surface area of ∼1300 m2/gMOF, which is comparable to reported surface areas of ∼1250–1600 m2/gMOF from conventional synthesis techniques, demonstrating good quality of the solvent-free MOF–fiber composites. We expect these results to extend vapor-phase MOF formation to new, practical substrates for advanced sensing and catalytic applications.
气相沸石咪唑酸盐框架-8 在纤维状聚合物基底上的生长
金属有机框架(MOFs)在实际应用中的使用往往受到合成相关挑战的阻碍。传统的溶液法依赖于有害溶剂,通常形成的粉末难以集成到实际设备中。另一方面,气相法通常会在硅基底上形成 MOF 薄膜,难以表征作为重要质量指标的 MOF 表面积。为了应对这些挑战,我们引入了一种无溶剂合成方法来形成 MOF-纤维复合材料,这种复合材料可以更容易地集成到器件中。此外,这些气相形成的 MOF-纤维复合材料与布鲁瑙尔-艾美特-泰勒表面积分析法兼容,可用于表征 MOF 的质量。我们利用原子层沉积在聚丙烯、聚酯和尼龙纤维基底上形成氧化锌薄膜,然后利用 2-甲基咪唑蒸气将其转化为沸石咪唑酸框架-8 (ZIF-8)。我们描述了氧化锌薄膜厚度和 MOF 转化条件对 MOF 结晶度和表面积的影响。我们报告的 ZIF-8 表面积为 ∼1300 m2/gMOF,与传统合成技术报告的表面积 ∼1250-1600 m2/gMOF相当,表明无溶剂 MOF 纤维复合材料的质量良好。我们期待这些结果能将气相 MOF 形成扩展到新的实用基底上,用于先进的传感和催化应用。
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