In Situ Energy-Dispersive X-ray Diffraction for the Synthesis Optimization and Scale-up of the Porous Zirconium Terephthalate UiO-66

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• 作者：Florence Ragon ; Patricia Horcajada ; Hubert Chevreau ; Young Kyu Hwang ; U-Hwang Lee ; Stuart R. Miller ; Thomas Devic ; Jong-San Chang ; Christian Serre
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：March 3, 2014
• 年：2014
• 卷：53
• 期：5
• 页码：2491-2500
• 全文大小：408K
• 年卷期：v.53,no.5(March 3, 2014)
• ISSN：1520-510X

文摘

The synthesis optimization and scale-up of the benchmarked microporous zirconium terephthalate UiO-66(Zr) were investigated by evaluating the impact of several parameters (zirconium precursors, acidic conditions, addition of water, and temperature) over the kinetics of crystallization by time-resolved in situ energy-dispersive X-ray diffraction. Both the addition of hydrochloric acid and water were found to speed up the reaction. The use of the less acidic ZrOCl₂路8H₂O as the precursor seemed to be a suitable alternative to ZrCl₄路xH₂O, avoiding possible reproducibility issues as a consequence of the high hygroscopic character of ZrCl₄. ZrOCl₂路8H₂O allowed the formation of smaller good quality UiO-66(Zr) submicronic particles, paving the way for their use within the nanotechnology domain, in addition to higher reaction yields, which makes this synthesis route suitable for the preparation of UiO-66(Zr) at a larger scale. In a final step, UiO-66(Zr) was prepared using conventional reflux conditions at the 0.5 kg scale, leading to a rather high space-time yield of 490 kg m^鈥? day^鈥?, while keeping physicochemical properties similar to those obtained from smaller scale solvothermally prepared batches.