Reactivity of Methoxy Species toward CO on Keggin 12-H3PW12O40: A Study with Solid State NMR

被引：31

作者：

Luzgin, Mikhail V. ^{[1
,2
]}

Kazantsev, Maxim S. ^{[2
]}

Wang, Wei ^{[3
]}

Stepanov, Alexander G. ^{[1
,2
]}

机构：

[1] Russian Acad Sci, Boreskov Inst Catalysis, Siberian Branch, Novosibirsk 630090, Russia

[2] Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia

[3] Lanzhou Univ, State Key Lab Appl Organ Chem, Coll Chem & Chem Engn, Lanzhou 730000, Gansu, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2009年 / 113卷 / 45期

基金：

中国国家自然科学基金; 俄罗斯基础研究基金会;

关键词：

INELASTIC NEUTRON-SCATTERING; VAPOR-PHASE CARBONYLATION; DIMETHYL ETHER; MAS-NMR; SELECTIVE CARBONYLATION; ALCOHOL DEHYDRATION; H-ZSM-5; ZEOLITE; CHEMICAL-SHIFTS; CARBENIUM IONS; C-13; CP/MAS;

D O I：

10.1021/jp906888m

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

By using C-13 solid-state NMR, monitoring the reactivity of methoxy species with carbon monoxide has been performed on 12-tungstophosphoric acid, H3PW12O40, at 423-473 K. Surface methoxy species have been selectively prepared from methanol at. 293-423 K. Almost quantitative conversion of surface methoxy species into acetyl groups bound to the Keggin anion and acetic acid has been observed at 473 K. These data provide unambiguous evidence for the role of methoxy species as the intermediate of methanol and dimethyl ether carbonylation on solid H3PW12O40. The formation of a trimethyloxonium ion has been detected on the surface of heteropolyacid for the first time. The carbonylation of trimethyloxonium proceeds via the analogous mechanism through the methoxy species intermediate.

引用

页码：19639 / 19644

页数：6

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