For decades the steric effect was still ambiguously understood in catalytic benzylation reactions of arenes with benzyl alcohol, which limited the green synthesis of phenylmethane derivates in industrial scale. This research applies a series of silica–alumina beta zeolites to systematically evaluate factors like catalyst porosity, reactants molecule size, and reaction temperature on catalytic benzylation. First, a suitable hierarchical beta zeolite catalyst was screened out by X-ray powder diffraction, N2
adsorption−desorption, and probe benzylation with p
-xylene. In the following substrates expanding study, for a typical benzylation of benzene, it showed extraordinary performance among literature reported ones that the conversion was 98% while selectivity was 90% at 353 K only after 10 min. The steric effect of aromatics with different molecular sizes on benzylation was observed. The reaction activities of four different aromatics followed the order: benzene > toluene > p
-xylene > mesitylene. Combined with macroscopic kinetic analysis, this comprehensive study points out for the first time that the nature of this steric effect was dominated by the relative adsorption efficiency of different guest aromatic molecules on the host zeolite surface.
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