Synergistic Effect between Zr-MOF and Phosphomolybdic Acid with the Promotion of TiF4 Template

• Published in: Molecules (Basel, Switzerland) Switzerland), 2020-10, Vol.25 (20), p.4673
• Main Authors: Ding, Zhu, Zhang, Xiao Min, Chang, Xue, Wang, Shuo, Wang, Dan-Hong, Zhang, Ming Hui, Zhang, Tian Hao
• Format: Article
• Language: English
• Subjects: Catalysts; Color; Crude oil; Desulfurization; Desulfurizing; Fluorides - chemistry; Fourier transforms; Free radicals; High temperature; Infrared spectroscopy; Metal oxides; Metal-organic frameworks; Metal-Organic Frameworks - chemistry; Microscopy, Electron, Scanning; Microscopy, Electron, Transmission; MOF materials; Molybdenum - chemistry; Organometallic Compounds - chemistry; oxidative desulfurization; Phosphomolybdic acid; Phosphoric Acids - chemistry; Photoelectron Spectroscopy; Phthalic Acids - chemistry; Raman spectroscopy; Reaction mechanisms; SMSI; Spectroscopy, Fourier Transform Infrared; Spectrum Analysis, Raman; Synergistic effect; TiF4-PU; Titanium - chemistry; X ray photoelectron spectroscopy; X-Ray Diffraction; Zirconium; Zr-MOF
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules25204673

Metal-Organic Framework (MOF) materials are often modified or functionalized, and then the crystal size and morphology of MOF materials are changed. In the process of preparing UiO-66 confined phosphomolybdic acid (PMA) composites (PU), the TiF -modified PU (PMA + UiO-66) composite catalyst (TiF -PU) was successfully synthesized by adding titanium tetrafluoride, and the catalytic desulfurization activity was excellent. Similarly, the reaction mechanism was investigated by means of infrared spectroscopy, Raman spectroscopy, XPS, and UV/Vis spectroscopy. The results show that the addition of TiF not only changes the appearance and color of the catalyst, but also changes the valence distribution of the elements in the catalyst. The number of oxygen vacancies in the MOF increases due to the addition of TiF , and more electrons are transferred from the Zr-MOF to PMA to form more Mo , which improved the performance of oxidative desulfurization in comparison. Thus, a stronger strong metal-support interaction (SMSI) effect is observed for TiF -modified PU catalysts. In addition, the quenching experiment of free radicals shows that ·OH radical is the main active substance in the oxidative desulfurization reaction over TiF -PU catalyst.