Yuan Hongye, Fu Weichu, Soulmi Nadia, Serre Christian, Steunou Nathalie, Rosso Michel, Henry de Villeneuve Catherine
Laboratoire de Physique de la Matière Condensée, CNRS, Ecole Polytechnique, Institut Polytechnique de Paris, 91120, Palaiseau, France.
Present address: State Key Laboratory for Mechanical Behavior of Materials, Shaanxi International Research Center for Soft Matter, School of Materials Science and Engineering, Xi'an Jiaotong University, Xi'an, 710049, P. R. China.
Chem Asian J. 2022 Jul 1;17(13):e202200129. doi: 10.1002/asia.202200129. Epub 2022 May 23.
The realization of metal-organic framework (MOF) layers onto solid surfaces is a prerequisite for their integration into devices. This work reports the direct growth of Fe /benzene di-carboxylate MOFs onto functionalized silicon surfaces, compatible with a wide range of MOF synthesis conditions. The co-nucleation and growth of different crystalline phases are evidenced, whose coverage depends on the surface chemistry and/or the solution composition. Three structural phases - the cubic MIL-101(Fe), a hexagonal phase with a structure close to MOF-235 and a MIL-53(Fe) with a monoclinic symmetry - are identified through characteristic crystal shapes and their structural parameters inferred from X-Ray Diffraction. In addition to the oriented growth of 3D crystallites, the formation of two-dimensional MIL-101 nano-crystallites or thin layers/islands exhibiting extended monocrystalline domains with (111) texture is also demonstrated through high-resolution atomic force microscopy. Post-synthesis treatments reveal a weak adhesion of the hexagonal phase, indicating a different surface anchoring.
在固体表面实现金属有机框架（MOF）层是将其集成到设备中的前提条件。这项工作报道了Fe/苯二甲酸酯MOF在功能化硅表面上的直接生长，这与广泛的MOF合成条件兼容。不同晶相的共成核和生长得到了证实，其覆盖范围取决于表面化学性质和/或溶液组成。通过特征晶体形状及其从X射线衍射推断出的结构参数，确定了三种结构相——立方相MIL-101(Fe)、结构接近MOF-235的六方相以及具有单斜对称性的MIL-53(Fe)。除了三维微晶的取向生长外，通过高分辨率原子力显微镜还证明了二维MIL-101纳米微晶或具有（111）织构的扩展单晶域的薄层/岛的形成。合成后处理显示六方相的附着力较弱，表明其表面锚固方式不同。
