点击次数：

论文类型：期刊论文

发表时间：2017-07-20

发表刊物：JOURNAL OF PHYSICAL CHEMISTRY C

收录刊物：SCIE、EI、Scopus

卷号：121

期号：28

页面范围：15248-15255

ISSN号：1932-7447

摘要：H-Beta zeolites with various Si/Al ratios have been prepared for the liquid-phase benzylation of various arenes with benzyl chloride (BzCI). Si-29 and Al-27 MAS NMR spectroscopy revealed the incorporation of Al into the silica framework to form catalytically active Bronsted acid sites (BAS). H-1 MAS NMR spectroscopy investigations demonstrated the BAS density increased with reducing Si/Al ratio, while the BAS strength decreased as probed by CD3CN molecules. These H-Beta zeolites are highly selective to desired monobenzylation products depending on the shape-selectivity induced by the suitable channel system. The catalytic performance is in line with the nudeophilicity and proton affinity (PA) of arenes (xylene > toluene > benzene) on the same catalyst, typically for Friedel-Crafts reaction. A shape-selective effect has been observed to dominate the reaction, lowering the performance of mesitylene compared to xylene, as well as being selective to only the monobenzylation product. The benzylation performance is enhanced with increasing the BAS strength of H-Beta zeolites due to the formation of more aryl cation intermediates by attacking electronegative chlorine atom in BzCl. An alternative reaction mechanism based on the activation of arenes by protonating aromatic ring of BAS is proposed to explain the superior benzylation activity of BzCI with less active arenes.