Chemical vapor deposition (CVD) is a rising tool to synthesize metal–organic framework (MOF) films. Despite growing interest and usage, its mechanism is less known. Especially, the identification of intermediates is crucial for understanding the growth mechanism and further controlling their structures. In this paper, we investigated the growth mechanism of 2D MOF Cu₃(C₆O₆)₂ film by CVD. We identified a novel intermediate phase: an octahedral coordination polymer that transforms into an edge-on-oriented 2D MOF. In situ grazing-incidence wide-angle X-ray scattering, X-ray absorption near-edge structure, high-resolution transmission electron microscopy, and Raman spectroscopy studies confirmed that this transformation involves the removal of pillars, leading to the formation of a square-planar 2D MOF. With the identification of intermediates, our study deepens the understanding of MOF film formation by CVD, which lays a foundation to control the structure.

中文翻译：

---

阐明化学气相沉积过程中配位聚合物中间体转化为 2D 金属-有机框架膜


化学气相沉积 （CVD） 是合成金属有机框架 （MOF） 薄膜的新兴工具。尽管人们的兴趣和使用越来越多，但其机制却鲜为人知。特别是，中间体的鉴定对于理解生长机制和进一步控制其结构至关重要。在本文中，我们研究了 CVD 制备的 2D MOF Cu₃（C₆O₆）₂ 薄膜的生长机制。我们确定了一种新的中间相：一种八面体配位聚合物，可转化为边缘定向的 2D MOF。原位掠入射广角 X 射线散射、X 射线吸收近边缘结构、高分辨率透射电子显微镜和拉曼光谱研究证实，这种转变涉及柱的去除，导致形成方形平面 2D MOF。随着中间体的鉴定，我们的研究加深了对 CVD 形成 MOF 薄膜的理解，为控制结构奠定了基础。