Methyl-Shield Cu-BTC with High Water Stability through One-Step Synthesis and In Situ Functionalization,Industrial & Engineering Chemistry Research

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Methyl-Shield Cu-BTC with High Water Stability through One-Step Synthesis and In Situ Functionalization
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2020-06-09 , DOI: 10.1021/acs.iecr.0c02156
Shanshan Xu _{1,

2} , Xiangyu Guo ₁ , Zhihua Qiao ₁ , Hongliang Huang ₁ , Chongli Zhong ₁

Affiliation

Cu-BTC is a copper paddlewheel-based metal–organic framework (MOF) with great potential in gas adsorption and heterogeneous catalysis but has restricted practical applications because of its poor water stability. In this work, we propose a strategy for one-step synthesis and in situ functionalization of isopropanol (IPA)-modified Cu-BTC (Cu-BTC-IPA) with enhanced water stability. Successful incorporation of IPA into Cu-BTC was evidenced by proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy spectra. The introduction of methyl groups around unsaturated Cu sites can form a methyl-shielding microenvironment, endowing Cu-BTC-IPA with the ability to maintain the topology structure after being immersed in water even for 4 days. After soaking, Cu-BTC-IPA can preserve 95% of its original Brunauer–Emmett–Teller (BET) surface areas and 90% of its initial CO₂ adsorption capacity, while Cu-BTC completely lost its crystallinity. In addition, Cu-BTC-IPA managed to preserve its main crystal structure and 83% of its initial BET surface areas after 12 h of immersion in diluted HCl solution (pH = 3). The improved hydrolysis stability mechanism of Cu-BTC-IPA was investigated using density functional theory calculations. The results suggest that the strategy of incorporating IPA into Cu-BTC is very efficient in enhancing its structure stability against water and worthy of further exploitation in improving the structure stability of other MOFs with open metal sites.

中文翻译：

通过一步合成和原位官能化具有高水稳定性的甲基屏蔽Cu-BTC

Cu-BTC是一种基于铜桨轮的金属有机框架（MOF），在气体吸附和非均相催化方面具有巨大潜力，但由于其水稳定性差，因此在实际应用中受到限制。在这项工作中，我们提出了一步合成和原位合成的策略异丙醇（IPA）改性的Cu-BTC（Cu-BTC-IPA）的功能化，具有增强的水稳定性。质子核磁共振光谱，傅立叶变换红外光谱和X射线光电子能谱证明了IPA成功地结合到Cu-BTC中。在不饱和铜位点周围引入甲基可形成甲基屏蔽微环境，赋予Cu-BTC-IPA浸入水中甚至4天后仍能保持拓扑结构的能力。浸泡后，Cu-BTC-IPA可以保留其原始Brunauer-Emmett-Teller（BET）表面积的95％和其初始CO _2的90％Cu-BTC完全失去了结晶性。此外，在稀释的HCl溶液（pH = 3）中浸泡12小时后，Cu-BTC-IPA设法保留了其主要晶体结构和83％的初始BET表面积。利用密度泛函理论计算研究了改进的Cu-BTC-IPA水解稳定性机理。结果表明，将IPA引入Cu-BTC的策略在增强其抗水结构稳定性方面非常有效，值得进一步开发，以改善其他具有开放金属位点的MOF的结构稳定性。

更新日期：2020-07-08

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