J Nanosci Nanotechnol. 2015 Dec;15(12):9369-81. doi: 10.1166/jnn.2015.11586.
Shape-Selective Catalysis in the Alkylation of Naphthalene: Steric Interaction with the Nanospace of Zeolites.
Journal of nanoscience and nanotechnology
Yoshihiro Sugi, Ajayan Vinu
PMID: 26682357
DOI: 10.1166/jnn.2015.11586
Abstract
Steric interaction of reagents with nanospace of zeolites was studied in alkylation: isopropylation, sec-butylation, and tert-butylation of naphthalene (NP) over several large-pore zeolites to elucidate the mechanism of shape-selective catalysis. Selectivities for β,β- and 2,6-dialkylnaphthalene (DAN) were influenced by the type of zeolite and bulkiness of alkylating agent. Shape-selective formation of β,β- and 2,6-diisopropylnaphthalene (DIPN) occurred only over H-mordenite (MOR) in the isopropylation of NP. Bulky α,α- and α,β-DIPN are excluded because of steric restriction at their transition states by the MOR channels, resulting in the selective formation of β,β- and 2,6-DIPN. AFI (SSZ-24) gave also high selectivities for 2,6-DIPN, and CFI (CIT-5) and MSE (MCM-68) gave high selectivities for β,β-DIPN. The lower selectivities for 2,6-DIPN were observed over the zeolites, ATS (SSZ-55), LFR (SSZ-42), DON (UTD-1), SFH (SSZ-53), FAU (Y-zeolite), BEA (zeolite β), and CON (CIT-1). Their channels allow the accommodation of bulky isomers, resulting in the catalysis under kinetic and/or thermodynamic controls. The selectivities for β,β- and 2,6-DAN were enhanced with the increase in bulkiness of alkylating agents: 1-butene for sec-butylation and 2-methylpropene for tert-butylation, even over zeolites with large pores and channels: the transition states of the least bulky isomers only fit the channels, and the other bulky isomers are excluded by steric restriction of the channels. However, tert-butylation over FAU, BEA, and CON had selectivities of around 50-60% for 2,6-DTBN, and almost 100% selectivities for β,β-DTBN. These zeolites cannot recognize the differences between 2,6- and 2,7-DTBN, but they can differentiate β,β-DTBN from the other isomers. The results indicate that the fitting of the least bulky isomers to zeolite channels, resulting in the exclusion of other bulky isomers, is a key for highly shape-selective catalysis.
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