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首页> 外文期刊>Crystal growth & design >Modulator Effects on the Water-Based Synthesis of Zr/Hf Metal-Organic Frameworks: Quantitative Relationship Studies between Modulator, Synthetic Condition, and Performance
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Modulator Effects on the Water-Based Synthesis of Zr/Hf Metal-Organic Frameworks: Quantitative Relationship Studies between Modulator, Synthetic Condition, and Performance

机译:调节剂对Zr / Hf金属有机骨架水基合成的影响:调节剂,合成条件和性能之间的定量关系研究

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摘要

The modulated synthesis of metal-organic frameworks (MOFs) remains empirical and challenging. Modulators are often applied and assumed capable of facilitating crystal growth by adjusting the reaction kinetics. However, most of the current studies are based on qualitative analysis and performance-leading synthesis, while no quantitative insights between modulator feature and MOF performance have been offered. In this work, we carried out a comprehensive study of the effects of three modulators (acetic acid, formic acid, trifluoroacetic acid) on the water-based modulated synthesis of UiO-66-type MOFs by using Zr or Hf as the building block and fumarate as the ligand. The modulator effects on crystallinity, yield, morphology, pore size, defects, porosity, stability, and gas separation performance of resultant MOFs have been discussed. A relationship between optimal molar ratio y and pK(a) value of modulator x is modeled as y = 12.72 + 0.193 X exp(1.276x). For MOF synthesis using ligands of different acidity, it tends to follow the equations of y = -40.78 + 39.1x and y = -21.7 + 25.58x for acetic acid and formic acid, respectively. Our results have thus provided pioneering quantitative analysis and synthetic guidelines on the further synthesis of water-stable MOFs that require modulators.
机译:金属有机骨架(MOF)的调制合成仍然是经验和挑战。通常使用调节剂,并假定调节剂能够通过调节反应动力学来促进晶体生长。但是,当前的大多数研究都基于定性分析和性能领先的综合技术,而调制器功能和MOF性能之间没有定量的见解。在这项工作中,我们以Zr或Hf为基石,对三种调节剂(乙酸,甲酸,三氟乙酸)对UiO-66型MOF的水基调制合成的影响进行了全面研究。富马酸酯作为配体。讨论了调节剂对所得MOF的结晶度,产率,形态,孔径,缺陷,孔隙率,稳定性和气体分离性能的影响。最佳摩尔比y与调制器x的pK(a)值之间的关系建模为y = 12.72 + 0.193 X exp(1.276x)。对于使用不同酸度的配体进行的MOF合成,乙酸和甲酸分别倾向于遵循y = -40.78 + 39.1x和y = -21.7 + 25.58x的方程。因此,我们的结果为进一步合成需要调节剂的水稳定性MOF提供了开创性的定量分析和合成指南。

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