Porous metal–organic frameworks have emerged to resolve important challenges of our modern society, such as CO₂ sequestration. Zeolitic imidazolate frameworks (ZIFs) can undergo a glass transition to form ZIF glasses; they combine the liquid handling of classical glasses with the tremendous potential for gas separation applications of ZIFs. Using millimetre-sized ZIF-62 single crystals and centimetre-sized ZIF-62 glass, we demonstrate the scalability and processability of our materials. Further, following the evolution of gas penetration into ZIF crystals and ZIF glasses by infrared microimaging techniques, we determine the diffusion coefficients and changes to the pore architecture on the ångström scale. The evolution of the material on melting and processing is observed in situ on different length scales by using a microscope-coupled heating stage and analysed microstructurally by transmission electron microscopy. Pore collapse during glass processing is further tracked by changes in the volume and density of the glasses. Mass spectrometry was utilized to investigate the crystal-to-glass transition and thermal-processing ability. The controllable tuning of the pore diameter in ZIF glass may enable liquid-processable ZIF glass membranes for challenging gas separations.

多孔金属有机框架的出现是为了解决现代社会的重要挑战，例如CO ₂封存。沸石咪唑酯骨架 (ZIF) 可以经历玻璃化转变形成 ZIF 玻璃；它们将经典玻璃的液体处理能力与 ZIF 气体分离应用的巨大潜力结合起来。使用毫米级 ZIF-62 单晶和厘米级 ZIF-62 玻璃，我们展示了材料的可扩展性和可加工性。此外，通过红外显微成像技术，随着气体渗透到 ZIF 晶体和 ZIF 玻璃的演变，我们确定了扩散系数和埃级孔隙结构的变化。通过使用显微镜耦合加热台在不同长度尺度上原位观察材料在熔化和加工过程中的演变，并通过透射电子显微镜进行微观结构分析。通过玻璃体积和密度的变化进一步跟踪玻璃加工过程中的孔塌陷。利用质谱法研究晶体到玻璃的转变和热处理能力。 ZIF 玻璃孔径的可控调节可以使可液体加工的 ZIF 玻璃膜能够用于具有挑战性的气体分离。