Nanoscale Synthesis of Two Porphyrin-Based MOFs with Gallium and Indium

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• 作者：Timo Rhauderwiek ; Steve Waitschat ; Stefan Wuttke ; Helge Reinsch ; Thomas Bein ; Norbert Stock
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5312-5319
• 全文大小：526K
• 年卷期：0
• ISSN：1520-510X

文摘

Two porphyrin-based metal–organic frameworks (MOFs) containing gallium or indium, [Ga₂(OH)₂(H₂TCPP)]·3DMF·3H₂O (Ga-PMOF) and [In₂(OH)₂(H₂TCPP)]·3DMF·4H₂O (In-PMOF) (H₆TCPP = 4-tetracarboxyphenylporphyrin), were discovered using high-throughput methods. The structure was refined by the Rietveld-method starting from the structure model of Al-PMOF, [Al₂(OH)₂(H₂TCPP)]. The new PMOFs exhibit BET surface areas between 1150 and 1400 m² g^–1 and are also porous toward CO₂ (Ga-PMOF, 15.2 wt %; In-PMOF, 12.9 wt %). They are thermally stable in air up to 330 °C, but show limited chemical stabilities toward acids and bases. In order to achieve size control, different synthesis routes were investigated, i.e., batch synthesis at different temperatures (yield: In-PMOF-bs-th 96%, Ga-PMOF-bs-th 87%), ultrasound-assisted synthesis (yield: In-PMOF-bs-us 85%), and continuous-flow synthesis (yield: Ga-PMOF-cf 71%). By using these different methods we could control the nucleation rate and the crystal size. The crystal sizes were found to vary about 60 to 160 nm and 70 to 130 nm for Ga- and In-PMOF, respectively, which was proven by dynamic light scattering (DLS), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements.