New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions

Maxym V. Vasylyev, Ronny Neumann

Research output: Contribution to journalArticle

214 Citations (Scopus)

Abstract

Inorganic-organic hybrid mesoporous materials were prepared by cocrystallization of a "sandwich" type polyoxometalate, [ZnWZn 2(H2O)2(ZnW9O34) 2]12-, and branched tripodal organic polyammonium salts, tris[2-(trimethylammonium)ethyl]-1,3,5-benzenetricarboxylate or 1,3,5-tris[4-(N,N,N-trimethylammonium-ethylcarboxyl)phenyl]benzene trications. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed formation of three-dimensional perforated coral-shaped amorphous materials with the organic cations surrounding polyoxometalate anions. N 2 sorption analysis showed that the hybrid materials have a BET surface area of ∼30-50 m2 g-1 and an average pore diameter of 36 Å leading to the classification of these materials as mesoporous materials with moderate surface areas. These hybrid materials behaved as very effective and selective heterogeneous catalysts for the epoxidation of allylic alcohols and oxidation of secondary alcohols to ketones with hydrogen peroxide as oxidant. The activity and selectivity of the heterogeneous catalysts based on the hybrid materials was similar to those of homogeneous catalysts based on the same [ZnWZn2(H2O) 2(ZnW9O34)2]12- polyoxometalate.

Original languageEnglish
Pages (from-to)884-890
Number of pages7
JournalJournal of the American Chemical Society
Volume126
Issue number3
DOIs
Publication statusPublished - Jan 28 2004

Fingerprint

Hybrid materials
Hydrogen peroxide
Hydrogen Peroxide
Oxidation
Catalysts
Mesoporous materials
Alcohols
Anthozoa
Epoxidation
Catalyst selectivity
Benzene
Ketones
Transmission Electron Microscopy
Oxidants
Electron Scanning Microscopy
Anions
Cations
Sorption
Catalyst activity
Negative ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions. / Vasylyev, Maxym V.; Neumann, Ronny.

In: Journal of the American Chemical Society, Vol. 126, No. 3, 28.01.2004, p. 884-890.

Research output: Contribution to journalArticle

@article{4937c5793f184cfd974282e506cc585e,
title = "New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions",
abstract = "Inorganic-organic hybrid mesoporous materials were prepared by cocrystallization of a {"}sandwich{"} type polyoxometalate, [ZnWZn 2(H2O)2(ZnW9O34) 2]12-, and branched tripodal organic polyammonium salts, tris[2-(trimethylammonium)ethyl]-1,3,5-benzenetricarboxylate or 1,3,5-tris[4-(N,N,N-trimethylammonium-ethylcarboxyl)phenyl]benzene trications. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed formation of three-dimensional perforated coral-shaped amorphous materials with the organic cations surrounding polyoxometalate anions. N 2 sorption analysis showed that the hybrid materials have a BET surface area of ∼30-50 m2 g-1 and an average pore diameter of 36 {\AA} leading to the classification of these materials as mesoporous materials with moderate surface areas. These hybrid materials behaved as very effective and selective heterogeneous catalysts for the epoxidation of allylic alcohols and oxidation of secondary alcohols to ketones with hydrogen peroxide as oxidant. The activity and selectivity of the heterogeneous catalysts based on the hybrid materials was similar to those of homogeneous catalysts based on the same [ZnWZn2(H2O) 2(ZnW9O34)2]12- polyoxometalate.",
author = "Vasylyev, {Maxym V.} and Ronny Neumann",
year = "2004",
month = "1",
day = "28",
doi = "10.1021/ja036702g",
language = "English",
volume = "126",
pages = "884--890",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions

AU - Vasylyev, Maxym V.

AU - Neumann, Ronny

PY - 2004/1/28

Y1 - 2004/1/28

N2 - Inorganic-organic hybrid mesoporous materials were prepared by cocrystallization of a "sandwich" type polyoxometalate, [ZnWZn 2(H2O)2(ZnW9O34) 2]12-, and branched tripodal organic polyammonium salts, tris[2-(trimethylammonium)ethyl]-1,3,5-benzenetricarboxylate or 1,3,5-tris[4-(N,N,N-trimethylammonium-ethylcarboxyl)phenyl]benzene trications. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed formation of three-dimensional perforated coral-shaped amorphous materials with the organic cations surrounding polyoxometalate anions. N 2 sorption analysis showed that the hybrid materials have a BET surface area of ∼30-50 m2 g-1 and an average pore diameter of 36 Å leading to the classification of these materials as mesoporous materials with moderate surface areas. These hybrid materials behaved as very effective and selective heterogeneous catalysts for the epoxidation of allylic alcohols and oxidation of secondary alcohols to ketones with hydrogen peroxide as oxidant. The activity and selectivity of the heterogeneous catalysts based on the hybrid materials was similar to those of homogeneous catalysts based on the same [ZnWZn2(H2O) 2(ZnW9O34)2]12- polyoxometalate.

AB - Inorganic-organic hybrid mesoporous materials were prepared by cocrystallization of a "sandwich" type polyoxometalate, [ZnWZn 2(H2O)2(ZnW9O34) 2]12-, and branched tripodal organic polyammonium salts, tris[2-(trimethylammonium)ethyl]-1,3,5-benzenetricarboxylate or 1,3,5-tris[4-(N,N,N-trimethylammonium-ethylcarboxyl)phenyl]benzene trications. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed formation of three-dimensional perforated coral-shaped amorphous materials with the organic cations surrounding polyoxometalate anions. N 2 sorption analysis showed that the hybrid materials have a BET surface area of ∼30-50 m2 g-1 and an average pore diameter of 36 Å leading to the classification of these materials as mesoporous materials with moderate surface areas. These hybrid materials behaved as very effective and selective heterogeneous catalysts for the epoxidation of allylic alcohols and oxidation of secondary alcohols to ketones with hydrogen peroxide as oxidant. The activity and selectivity of the heterogeneous catalysts based on the hybrid materials was similar to those of homogeneous catalysts based on the same [ZnWZn2(H2O) 2(ZnW9O34)2]12- polyoxometalate.

UR - http://www.scopus.com/inward/record.url?scp=1642494625&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=1642494625&partnerID=8YFLogxK

U2 - 10.1021/ja036702g

DO - 10.1021/ja036702g

M3 - Article

VL - 126

SP - 884

EP - 890

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 3

ER -