Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 3107 - 3118 (1981)
Update date:2022-08-16
Topics:
Matsuda, Tsuneo
Sato, Masahiro
Kanno, Tomoaki
Miura, Hiroshi
Sugiyama, Kazuo
On a variety of heteropoly compounds as catalysts the isomerization of but-1-ene and cis-but-2-ene was performed with the aim of examining the relationship between the acidic properties of the compounds and the method of pretreatment.Neither of the central atoms, P and Si, in the anions in these compounds affected the isomerization activity of but-1-ene, but the counter-cations and MoO6 or WO6 octahedra surrounding the central atom did affect the activity.The cis-but-2-ene to trans-but-2-ene ratio was greater than 3 on the heteropolymolybdate catalysts pretreated at temperatures lower than 150 deg C, and decreased with increasing pretreatment temperature until reaching a value of 1.In cis-but-2-ene isomerization Cu, Ni, Co and Mn salts of the heteropoly molybdates pretreated at 300 deg C showed an increase in the ratio of trans-but-2-ene to but-1-ene, which corresponds to the formation of strongly acidic sites, while Ba and Sr salts did not show a pronounced increase in the ratio.A linear correlation between this ratio and the electronegativity of the salt counter-cation was seen in the pretreatment at 300 deg C; the strongly acidic property is produced by the interaction of the counter-cation with the structural water, which is eliminated in the high-temperature range (200-250 deg C) used in d.t.a.But-2-enes containing deuterium were produced in the but-1-ene isomerization on the catalysts pretreated with D2O, indicating that the structural water also correlated with the formation of acidic sites on the catalysts.
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Doi:10.1021/ja01073a082
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