无溶剂条件下磷酸锆纳米粒子作为固体酸催化剂催化苯酚选择性烷基化(英文)  

Zirconium phosphate nanoparticles as a remarkable solid acid catalyst for selective solvent-free alkylation of phenol

作　　者：Abdol R. Hajipour Hirbod Karimi 

机构地区：[1]Pharmaceutical Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan 84156, IR Iran [2]Department of Neuroscience, University of Wisconsin, Medical School, Madison, W153706-1532, USA

出　　处：《催化学报》2014年第7期1136-1147,共12页

基　　金：We gratefully acknowledge the funding support received for this project from the Isfahan University of Technology (IUT), IR Iran. Further financial support from the Center of Excellence in Sensor and Green Chemistry Research (IUT) is gratefully acknowledged.

摘　　要：A facile synthesis of α-zirconium phosphate(ZP) nanoparticles as an effective, eco-friendly, and recyclable solid acid catalyst is reported. Polyvinylpyrrolidone(PVP) and polyvinyl alcohol(PVA) were used as organic matrix as dispersing agents and served as a template for the nanoparticles. Hydrogen bonds between ZP and PVA or PVP, along the polymer chains, appear to play an important role for improving the dispersion of in situ formed ZP. Following calcination of PVA/ZP or PVP/ZP, pure hexagonal ZP nanoparticles were obtained. The catalysts were characterized by nitrogen sorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy, and transmission electron microscopy. Pyridine-FTIR and temperature-programmed desorption of NH3 suggest the presence of Brnsted acid sites. The acidic properties of the catalyst were studied in Friedel-Crafts alkylation of phenol by tert-butanol, producing 2-tert-butylphenol, 4-tert-butylphenol, and 2,4-ditert-butylphenol. The alkylation reaction was performed in the presence of catalysts P2O5/Al2O3, P2O5/SiO2, α-ZrP(prepared in the absence of the polymers), and various ionic liquids. The use of the hexagonal ZP nanoparticle catalyst afforded an excellent phenol conversion(86%) and selectivity towards 4-tert-butylphenol(83%) under optimized reaction conditions. The catalyst was easily recovered from the reaction mixture, regenerated, and reused at least four times without significant loss in the catalytic activity.A facile synthesis of α-zirconium phosphate （ZP） nanoparticles as an effective, eco-friendly, and recyclable solid acid catalyst is reported. Polyvinylpyrrolidone （PVP） and polyvinyl alcohol （PVA） were used as organic matrix as dispersing agents and served as a template for the nanoparticles. Hydrogen bonds between ZP and PVA or PVP, along the polymer chains, appear to play an important role for improving the dispersion of in situ formed ZP. Following calcination of PVA/ZP or PVP/ZP, pure hexagonal ZP nanoparticles were obtained. The catalysts were characterized by nitrogen sorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy （FTIR）, scanning electron microscopy, and transmission elec-tron microscopy. Pyridine-FTIR and temperature-programmed desorption of NH3 suggest the presence of Br？nsted acid sites. The acidic properties of the catalyst were studied in Friedel-Crafts alkylation of phenol by tert-butanol, producing 2-tert-butylphenol, 4-tert-butylphenol, and 2,4-ditert-butylphenol. The alkylation reaction was performed in the presence of catalysts P2O5/Al2O3, P2O5/SiO2, α-ZrP （prepared in the absence of the polymers）, and various ionic liquids. The use of the hexagonal ZP nanoparticle catalyst afforded an excellent phenol conversion （86%） and selectivity towards 4-tert-butylphenol （83%） under optimized reaction conditions. The catalyst was easily recovered from the reaction mixture, regenerated, and reused at least four times without significant loss in the catalytic activity.

关 键 词：FRIEDEL-CRAFTS烷基化反应 二叔丁基苯酚 固体酸催化剂 纳米粒子 磷酸锆 选择性溶剂 电感耦合等离子体发射光谱法 扫描电子显微镜 

分 类 号：O643.36[理学—物理化学] TQ325.12[理学—化学]