Bauza Marta, Leo Pedro, Palomino Cabello Carlos, Martin Antonio, Orcajo Gisela, Turnes Palomino Gemma, Martinez Fernando
Department of Chemistry, University of the Balearic Islands, Cra. de Valldemossa, Palma de Mallorca 07122, Spain.
Chemical and Environmental Engineering Group. ESCET, Universidad Rey Juan Carlos. c/Tulipán s/n, Móstoles 28933, Spain.
Inorg Chem. 2024 Sep 23;63(38):17460-17468. doi: 10.1021/acs.inorgchem.4c01792. Epub 2024 Sep 3.
The catalytic activity and stability of sulfonic-based UiO-66(Zr) materials were tested in the Friedel-Crafts acylation of anisole with acetic anhydride. The materials were prepared using microwave-assisted synthesis, producing microporous materials with remarkable crystallinity and physicochemical features as acid catalysts. Different ratios between both organic ligands, terephthalic acid (HBDC) and monosodium 2-sulfoterephthalic acid (HBDC-SONa), were used for the synthesis to modulate the sulfonic content. The sulfonic-based UiO-66(Zr) material synthesized with a HBDC/HBDC-SONa molar ratio of 40/60 exhibited the best catalytic performance in the acidic-catalyzed Friedel-Crafts acylation reaction. This ratio balanced the number of sulfonic acid sites and their accessibility within the UiO-66 microporous structure. The catalytic performance of this material increased remarkably at 200 °C, outperforming reference acids and commercial heterogeneous catalysts such as Nafion-SAC-13 and Amberlyst-70. Additionally, the best sulfonic-based UiO-66(Zr) material proved to be stable in four successive reaction cycles, maintaining both its catalytic activity and its structural integrity.
在苯甲醚与乙酸酐的傅克酰基化反应中测试了磺酸基UiO-66(Zr)材料的催化活性和稳定性。这些材料采用微波辅助合成法制备，得到具有显著结晶度和物理化学特性的微孔材料作为酸催化剂。合成过程中使用了两种有机配体对苯二甲酸（HBDC）和2-磺酸基对苯二甲酸钠（HBDC-SONa）的不同比例来调节磺酸含量。HBDC/HBDC-SONa摩尔比为40/60合成的磺酸基UiO-66(Zr)材料在酸催化的傅克酰基化反应中表现出最佳催化性能。该比例平衡了UiO-66微孔结构内磺酸位点的数量及其可及性。该材料在200°C时催化性能显著提高，优于参考酸和商业非均相催化剂如Nafion-SAC-13和Amberlyst-70。此外，最佳的磺酸基UiO-66(Zr)材料在四个连续反应循环中被证明是稳定的，保持了其催化活性和结构完整性。
