Cu/ZnO aggregates in siliceous mesoporous matrices: Development of a new model methanol synthesis catalyst

Research output: Contribution to journal › Article › Research › peer review

Authors

  • M. W.E. van den Berg
  • S. Polarz
  • O. P. Tkachenko
  • K. V. Klementiev
  • M. Bandyopadhyay
  • L. Khodeir
  • H. Gies
  • M. Muhler
  • W. Grünert

External Research Organisations

  • Ruhr-Universität Bochum
  • Technische Universität Berlin
  • Deutsches Elektronen-Synchrotron (DESY)
View graph of relations

Details

Original languageEnglish
Pages (from-to)446-455
Number of pages10
JournalJournal of catalysis
Volume241
Issue number2
Early online date22 Jun 2006
Publication statusPublished - 25 Jul 2006
Externally publishedYes

Abstract

Copper and zinc were introduced into mesoporous siliceous matrices with the goal of obtaining model methanol synthesis catalysts with intense interaction between copper and the ZnO promoter. The preparation methods included various aqueous routes starting from acetate solutions (into MCM-48) and a route involving an organometallic step-thermolysis of a liquid heterocubane of Zn4O4 type ([CH3ZnOCH2CH2OCH3]4) in a wormhole-type silica of 5 nm average pore size-followed by aqueous Cu (nitrate) impregnation. The materials were characterized by XRD, nitrogen physisorption, N2O frontal chromatography, TPR, and EXAFS, and their methanol synthesis activity was measured at 493 K and normal pressure. In the aqueous preparations with acetate solutions, excessive formation of silicates (particularly zinc silicate) led to damage of the pore system. A significant delay in Cu reduction was assigned to the influence of micropores formed, together with some copper silicate formation. These samples exhibited poorly accessible Cu surface areas despite small Cu particle sizes indicated by EXAFS and disappointing methanol synthesis activity. In contrast to this, a highly active catalyst was obtained via the heterocubane route that meets industrial standards in terms of reaction rate per Cu surface area. Orientation studies (EXAFS at the CuK and ZnK edges) reflecting a redox behavior of the ZnOx component illustrate the potential of this catalyst type for use in basic studies of the Cu-ZnOx interaction in methanol synthesis catalysts.

Keywords

    Copper, MCM-48, Mesoporous silica, Metal-support interaction, Methanol synthesis, Model catalyst, TPR, XAFS, Zinc oxide

ASJC Scopus subject areas

Cite this

Cu/ZnO aggregates in siliceous mesoporous matrices: Development of a new model methanol synthesis catalyst. / van den Berg, M. W.E.; Polarz, S.; Tkachenko, O. P. et al.
In: Journal of catalysis, Vol. 241, No. 2, 25.07.2006, p. 446-455.

Research output: Contribution to journal › Article › Research › peer review

van den Berg, MWE, Polarz, S, Tkachenko, OP, Klementiev, KV, Bandyopadhyay, M, Khodeir, L, Gies, H, Muhler, M & Grünert, W 2006, 'Cu/ZnO aggregates in siliceous mesoporous matrices: Development of a new model methanol synthesis catalyst', Journal of catalysis, vol. 241, no. 2, pp. 446-455. https://doi.org/10.1016/j.jcat.2006.05.020
van den Berg, M. W. E., Polarz, S., Tkachenko, O. P., Klementiev, K. V., Bandyopadhyay, M., Khodeir, L., Gies, H., Muhler, M., & Grünert, W. (2006). Cu/ZnO aggregates in siliceous mesoporous matrices: Development of a new model methanol synthesis catalyst. Journal of catalysis, 241(2), 446-455. https://doi.org/10.1016/j.jcat.2006.05.020
van den Berg MWE, Polarz S, Tkachenko OP, Klementiev KV, Bandyopadhyay M, Khodeir L et al. Cu/ZnO aggregates in siliceous mesoporous matrices: Development of a new model methanol synthesis catalyst. Journal of catalysis. 2006 Jul 25;241(2):446-455. Epub 2006 Jun 22. doi: 10.1016/j.jcat.2006.05.020
van den Berg, M. W.E. ; Polarz, S. ; Tkachenko, O. P. et al. / Cu/ZnO aggregates in siliceous mesoporous matrices : Development of a new model methanol synthesis catalyst. In: Journal of catalysis. 2006 ; Vol. 241, No. 2. pp. 446-455.
Download
@article{aaf885f48c11480781146749547180a7,
title = "Cu/ZnO aggregates in siliceous mesoporous matrices: Development of a new model methanol synthesis catalyst",
abstract = "Copper and zinc were introduced into mesoporous siliceous matrices with the goal of obtaining model methanol synthesis catalysts with intense interaction between copper and the ZnO promoter. The preparation methods included various aqueous routes starting from acetate solutions (into MCM-48) and a route involving an organometallic step-thermolysis of a liquid heterocubane of Zn4O4 type ([CH3ZnOCH2CH2OCH3]4) in a wormhole-type silica of 5 nm average pore size-followed by aqueous Cu (nitrate) impregnation. The materials were characterized by XRD, nitrogen physisorption, N2O frontal chromatography, TPR, and EXAFS, and their methanol synthesis activity was measured at 493 K and normal pressure. In the aqueous preparations with acetate solutions, excessive formation of silicates (particularly zinc silicate) led to damage of the pore system. A significant delay in Cu reduction was assigned to the influence of micropores formed, together with some copper silicate formation. These samples exhibited poorly accessible Cu surface areas despite small Cu particle sizes indicated by EXAFS and disappointing methanol synthesis activity. In contrast to this, a highly active catalyst was obtained via the heterocubane route that meets industrial standards in terms of reaction rate per Cu surface area. Orientation studies (EXAFS at the CuK and ZnK edges) reflecting a redox behavior of the ZnOx component illustrate the potential of this catalyst type for use in basic studies of the Cu-ZnOx interaction in methanol synthesis catalysts.",
keywords = "Copper, MCM-48, Mesoporous silica, Metal-support interaction, Methanol synthesis, Model catalyst, TPR, XAFS, Zinc oxide",
author = "{van den Berg}, {M. W.E.} and S. Polarz and Tkachenko, {O. P.} and Klementiev, {K. V.} and M. Bandyopadhyay and L. Khodeir and H. Gies and M. Muhler and W. Gr{\"u}nert",
note = "Funding Information: The work was funded by the German Science Foundation (DFG) in the framework of the Collaborative Research Center “Metal–Substrate Interactions in Heterogeneous Catalysis” (SFB 558), which is gratefully acknowledged. The authors thank Mrs. Susanne Buse for performing the TPR measurements and porosity analyses. ",
year = "2006",
month = jul,
day = "25",
doi = "10.1016/j.jcat.2006.05.020",
language = "English",
volume = "241",
pages = "446--455",
journal = "Journal of catalysis",
issn = "0021-9517",
publisher = "Academic Press Inc.",
number = "2",

}

Download

TY - JOUR

T1 - Cu/ZnO aggregates in siliceous mesoporous matrices

T2 - Development of a new model methanol synthesis catalyst

AU - van den Berg, M. W.E.

AU - Polarz, S.

AU - Tkachenko, O. P.

AU - Klementiev, K. V.

AU - Bandyopadhyay, M.

AU - Khodeir, L.

AU - Gies, H.

AU - Muhler, M.

AU - Grünert, W.

N1 - Funding Information: The work was funded by the German Science Foundation (DFG) in the framework of the Collaborative Research Center “Metal–Substrate Interactions in Heterogeneous Catalysis” (SFB 558), which is gratefully acknowledged. The authors thank Mrs. Susanne Buse for performing the TPR measurements and porosity analyses.

PY - 2006/7/25

Y1 - 2006/7/25

N2 - Copper and zinc were introduced into mesoporous siliceous matrices with the goal of obtaining model methanol synthesis catalysts with intense interaction between copper and the ZnO promoter. The preparation methods included various aqueous routes starting from acetate solutions (into MCM-48) and a route involving an organometallic step-thermolysis of a liquid heterocubane of Zn4O4 type ([CH3ZnOCH2CH2OCH3]4) in a wormhole-type silica of 5 nm average pore size-followed by aqueous Cu (nitrate) impregnation. The materials were characterized by XRD, nitrogen physisorption, N2O frontal chromatography, TPR, and EXAFS, and their methanol synthesis activity was measured at 493 K and normal pressure. In the aqueous preparations with acetate solutions, excessive formation of silicates (particularly zinc silicate) led to damage of the pore system. A significant delay in Cu reduction was assigned to the influence of micropores formed, together with some copper silicate formation. These samples exhibited poorly accessible Cu surface areas despite small Cu particle sizes indicated by EXAFS and disappointing methanol synthesis activity. In contrast to this, a highly active catalyst was obtained via the heterocubane route that meets industrial standards in terms of reaction rate per Cu surface area. Orientation studies (EXAFS at the CuK and ZnK edges) reflecting a redox behavior of the ZnOx component illustrate the potential of this catalyst type for use in basic studies of the Cu-ZnOx interaction in methanol synthesis catalysts.

AB - Copper and zinc were introduced into mesoporous siliceous matrices with the goal of obtaining model methanol synthesis catalysts with intense interaction between copper and the ZnO promoter. The preparation methods included various aqueous routes starting from acetate solutions (into MCM-48) and a route involving an organometallic step-thermolysis of a liquid heterocubane of Zn4O4 type ([CH3ZnOCH2CH2OCH3]4) in a wormhole-type silica of 5 nm average pore size-followed by aqueous Cu (nitrate) impregnation. The materials were characterized by XRD, nitrogen physisorption, N2O frontal chromatography, TPR, and EXAFS, and their methanol synthesis activity was measured at 493 K and normal pressure. In the aqueous preparations with acetate solutions, excessive formation of silicates (particularly zinc silicate) led to damage of the pore system. A significant delay in Cu reduction was assigned to the influence of micropores formed, together with some copper silicate formation. These samples exhibited poorly accessible Cu surface areas despite small Cu particle sizes indicated by EXAFS and disappointing methanol synthesis activity. In contrast to this, a highly active catalyst was obtained via the heterocubane route that meets industrial standards in terms of reaction rate per Cu surface area. Orientation studies (EXAFS at the CuK and ZnK edges) reflecting a redox behavior of the ZnOx component illustrate the potential of this catalyst type for use in basic studies of the Cu-ZnOx interaction in methanol synthesis catalysts.

KW - Copper

KW - MCM-48

KW - Mesoporous silica

KW - Metal-support interaction

KW - Methanol synthesis

KW - Model catalyst

KW - TPR

KW - XAFS

KW - Zinc oxide

UR - http://www.scopus.com/inward/record.url?scp=33745354650&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2006.05.020

DO - 10.1016/j.jcat.2006.05.020

M3 - Article

AN - SCOPUS:33745354650

VL - 241

SP - 446

EP - 455

JO - Journal of catalysis

JF - Journal of catalysis

SN - 0021-9517

IS - 2

ER -