Real-Space Imaging of the Molecular Changes in Metal-Organic Frameworks under Electron Irradiation.

Electron-induced structural changes influence the characterizations of the local structure of various materials by electron microscope. However, for beam-sensitive materials, it is still challenging to detect such changes by electron microscopy, which may help us quantitatively reveal how electrons interact with materials under electron irradiation. Here, we use an emergent phase contrast technique in electron microscopy to clearly image a metal-organic framework, UiO-66 (Zr), at an ultralow electron dose and dose rate. The effects of both the dose and dose rate on the UiO-66 (Zr) structure are visualized, which induce obvious missing organic linkers. The kinetics of the missing linker based on the radiolysis mechanism are semiquantitatively expressed by the different intensities of the imaged organic linkers. Deformation of the UiO-66 (Zr) lattice after the missing linker is also observed. These observations make it possible to visually investigate the electron-induced chemistry in various beam-sensitive materials and avoid electron damage to them.