Liu Pingying, Tian Ziqi, Chen Liang
School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen, Jiangxi 333403, P. R. China.
Ningbo Institute of Materials Technology and Engineering Chinese Academy of Sciences, Ningbo, Zhejiang 315201, P. R. China.
ACS Appl Mater Interfaces. 2022 Jul 20;14(28):32009-32017. doi: 10.1021/acsami.2c07124. Epub 2022 Jul 7.
Smart metal-organic frameworks (MOFs) are constructed by introducing stimuli-responsive functional groups into MOF platforms. Through membrane systems containing smart MOFs, external field-modulated gas transport can be achieved, which finds potential applications in chemical engineering. In this work, we design a series of Mg-MOF-74-III-based frameworks functionalized by arylazopyrazole groups. Methyleneamine chains with various lengths are attached to the photoresponsive azopyrazole moiety. Molecular dynamics simulations show that CO diffusion can be remarkably changed by controlling the -to- isomerization of the functional unit due to the tunable adsorbate-adsorbent and adsorbate-adsorbate interactions of the two states. With the optimal length of the functional chain, the spatial hindrance and adsorbate-adsorbent interaction exhibit a synergetic effect to maximize the stimuli-responsive kinetic separation of N over CO. This work provides a promising strategy for elevating smart MOFs' potential in gas separation.
智能金属有机框架材料（MOFs）是通过将刺激响应性功能基团引入MOF平台构建而成。通过包含智能MOFs的膜系统，可以实现外部场调制的气体传输，这在化学工程中具有潜在应用。在这项工作中，我们设计了一系列由芳基偶氮吡唑基团功能化的基于Mg-MOF-74-III的框架材料。不同长度的甲胺链连接到光响应性偶氮吡唑部分。分子动力学模拟表明，由于两种状态下可调的吸附质-吸附剂和吸附质-吸附质相互作用，通过控制功能单元的顺反异构化可以显著改变CO的扩散。在功能链长度最佳时，空间位阻和吸附质-吸附剂相互作用呈现协同效应，以使N相对于CO的刺激响应动力学分离最大化。这项工作为提升智能MOFs在气体分离方面的潜力提供了一种有前景的策略。
