Sonochemical synthesis of Zr-based porphyrinic MOF-525 and MOF-545: Enhancement in catalytic and adsorption properties

• Published in: Microporous and mesoporous materials 2021-03, Vol.316, p.110985, Article 110985
• Main Authors: Yu, Kwangsun, Lee, Yu-Ri, Seo, Jin Young, Baek, Kyung-Youl, Chung, Young-Min, Ahn, Wha-Seung
• Format: Article
• Language: English
• Subjects: Bisphenol-A adsorption; DMNP hydrolysis; MOF-525; MOF-545; Sonochemical synthesis
• ISSN: 1387-1811; 1873-3093
• DOI: 10.1016/j.micromeso.2021.110985

The synthesis of metal-organic frameworks (MOFs) with in-built porphyrin units remains challenging. It takes long synthesis time under carefully controlled reaction conditions, and a mixed-phase with different crystal morphologies is still frequently observed. In this work, Zr-based porphyrinic MOF-525 and MOF-545 in high purity and uniform size were produced through a sonochemical route in 2.5 and 0.5 h, respectively, using zirconyl chloride octahydrate and tetrakis (4-carboxyphenyl) porphyrin. Benzoic acid was used as a modulator for MOF-525, and trifluoroacetic acid for MOF-545. The physicochemical properties of the MOF products were examined by X-ray diffraction, scanning electron microscopy, and N2 adsorption-desorption isotherms. Additionally, the defect sites in the MOF samples were analyzed by UV–vis spectrometry, thermogravimetric analysis, and inductively coupled plasma mass spectrometer. The sonochemically synthesized MOF samples had more defect sites than the conventionally prepared ones and exhibited improved textural properties. In particular, the MOF-545 had a significantly smaller (ca. 1.0 μm) particle size than the conventionally prepared sample (ca. 4.8 μm). The MOF-525 and MOF-545 prepared by the sonochemical route exhibited enhanced hydrolysis of the chemical warfare simulant dimethyl-4-nitrophenyl phosphate (DMNP) and a faster and higher bisphenol-A adsorption than the conventionally prepared MOF samples. MOF-525 and MOF-545 were synthesized through a sonochemical route and tested for the hydrolysis of DMNP and adsorption of BPA. [Display omitted] •Sonochemical syntheses of zirconium-based porphyrinic MOF 525 and 545 were reported.•High-purity crystals of MOF-525 and MOF-545 were obtained within 2.5 h and 0.5 h, respectively.•These MOFs were tested for the hydrolysis of dimethyl-4-nitrophenyl phosphate (DMNP) and adsorption of bisphenol-A (BPA).•Enhanced performances of these MOFs due to increased defect sites, smaller particles size, and larger BET surface area.