Transformation of Amorphous Terbium Metal–Organic Framework on Terbium Oxide TbOx(111) Thin Film on Pt(111) Substrate: Structure of TbxOy Film

• Published in: Nanomaterials (Basel, Switzerland) Switzerland), 2022-08, Vol.12 (16), p.2817
• Main Authors: Brunckova, Helena, Mudra, Erika, Streckova, Magdalena, Medvecky, Lubomir, Sopcak, Tibor, Shepa, Ivan, Kovalcikova, Alexandra, Lisnichuk, Maksym, Kolev, Hristo
• Format: Article
• Language: English
• Subjects: Acetic acid; Amorphous structure; amorphous TbMOF; Atomic force microscopy; Calorimetry; Catalysis; Chemical composition; Crystal structure; Crystallinity; Crystallites; Crystals; Decomposition; Differential scanning calorimetry; Electron microscopy; Fluorite; Fourier transforms; Hydrocarbons; Infrared spectroscopy; Interlayers; Metal-organic frameworks; microstructure; Nanocrystals; Nitrates; Oxide coatings; Phase transitions; Photoelectron spectroscopy; Photoelectrons; Pyrolysis; Raman spectroscopy; Scanning electron microscopy; Sensors; Silicon dioxide; Silicon substrates; Sodium acetate; solvothermal synthesis; Spectroscopy; Spectrum analysis; Synthesis; Terbium; terbium oxide; Thermogravimetry; thin film; Thin films; Transmission electron microscopy; X ray photoelectron spectroscopy; X-ray diffraction
• ISSN: 2079-4991; 2079-4991
• DOI: 10.3390/nano12162817

The present study is focused on the synthesis and structural properties of amorphous terbium metal–organic framework thin film (TbMOF-TF) and its transformation to terbium oxide by pyrolysis at 450 °C in the air. The crystalline (cTbMOF) and amorphous (aTbMOF) films were prepared by solvothermal synthesis using different amounts (0.4 and 0.7 mmol) of the modulator (sodium acetate), respectively. The powders were characterized by differential scanning calorimetry (DSC), thermogravimetry (TG), Fourier transform infrared (FTIR), Raman spectroscopy, and scanning electron microscopy (SEM). The varied chemical composition of the surface of TbMOFs and TbxOy was investigated by X-ray photoelectron spectroscopy (XPS). X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed that aTbMOF had been fully transformed to a Tb4O7 phase with a cubic crystal structure at 450 °C. The amorphous aTbMOF-TF film was prepared by dropping a colloidal solution of amorphous precursor nanocrystals on the SiO2/Si substrates covered with Pt as an interlayer. XPS confirmed the presence of Tb in two states, Tb3+ and Tb4+. The amorphous film has a rough, porous microstructure and is composed of large clusters of worm-like particles, while terbium oxide film consists of fine crystallites of cubic fluorite cF-TbOx, c-Tb4O7, and c-Tb2O3 phases. The surface topography was investigated by a combination of confocal (CM) and atomic force microscopy (AFM). The amorphous film is porous and rough, which is contrast to the crystalline terbium oxide film.