zirconium

1206 Words3 Pages

2.1 Materials
All Chemicals and solvents were purchased from Sigma-Aldrich and Merck Chemical Companies and used without further purification.
2.2 Catalyst synthesis
A 10% solution of PVA (Mw = 70000) was prepared by dissolving of PVA in deionized hot water (95 °C). The pH value was adjusted about pH=3, by adding HCl. To prevent thermal decomposition and monitor the temperature of the PVA solution, a water bath was used. 50 ml of a 1 M solution of ZrOCl2.8H2O added dropwise to precursor solution and heated at the 60 °C for 2 h with constant stirring using a magnetic stirrer that leads to a better dispersion of Zr4+ ions into the polymer chains. To the resulted homogeneous solution, under ultrasonication, 50 ml of 2 M H3PO4 added dropwise at 50-60 °C for 2 h. On addition of phosphoric acid, Zr4+ ions reacted with PO43− ions almost immediately to form in situ ZP. The resulted mixture was allowed to age for 6 h, then the precipitate was filtered and washed with distilled water several times and dried in an oven at 80 °C overnight. The obtained white colored fluffy precursor was ground and calcined at the 550 °C for 4 h to decompose the organic matrix. The final product, the desired pure ZP nanocrystals, was identified as ZPA. A 10% solution of PVP (Mw = 40000) was prepared by dissolving PVP in deionized water. After this, the same procedure, as described in the above, was performed to produce ZP anoparticles. The final product was identified as ZPP. The summarized procedure is presented in Scheme 1.

Scheme 1. Summarized process of α-zirconium phosphate nanoparticles (ZPA and ZPP) preparation.
The detailed procedure for the preparation of the α-ZrP can be found in the literature [28]. P2O5/Al2O3 [54], P2O5/SiO2 [55], 1-H-3-methyl-im...

... middle of paper ...

... solid catalysts is known to occur either by the adsorption of both the aromatic and the alkylating agent molecules on the surface i.e., by a Langmuir–Hinshelwood (LH) mechanism or by the reaction of the adsorbed alkylating agent with aromatic molecules in gas phase, i.e., by an Eley–Rideal (ER) mechanism [59-62].

Scheme 3. H-bonds interactions between polymers and the P-OH groups of ZP.
It seems TBA and phenol adsorbed on the ZPA (or ZPP) surface due to hydrogen bondings. In the presence of ZPA (or ZPP) as solid acid catalyst, TBA turns to tert-butyloxonium which is so reactive toward nucleophiles, such as phenol, which produces 2-TBP, 4-TBP and 2,4-DTBP, Scheme 3. The main advantage of ZPA (or ZPP) as an alkylating catalyst, in comparison with other catalysts, is that it can significantly influence the product selectivity due to its uniform structure (scheme 4).

More about zirconium

Open Document