Citation: Abdol R. Hajipour, Hirbod Karimi. Zirconium phosphate nanoparticles as a remarkable solid acid catalyst for selective solvent-free alkylation of phenol[J]. Chinese Journal of Catalysis, ;2014, 35(7): 1136-1147. doi: 10.1016/S1872-2067(14)60060-7 shu

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

Abdol R. Hajipour ^a,b,, ,
Hirbod Karimi ^a

1.
a. Pharmaceutical Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan 84156, IR Iran;

Corresponding author: Abdol R. Hajipour,
Received Date: 6 December 2013
Available Online: 20 February 2014

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 Brönsted 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-di-tert-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.
- Hexagonal zirconium phosphate,
- Nanoparticle,
- Solvent free Phenol alkylation,
- eterogeneous catalyst,
- Polyvinyl alcohol,
- Polyvinylpyrrolidone
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