IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer
Abstract
Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm-1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Znδ+–CO. The presence of not completely reduced Cuδ+–CO species cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm-1 due to nano-structured Cu0–CO and CO adsorbed on highly defective Cu0, respectively, indicate that the coverage of metallic copper is not complete.
- Authors:
-
- Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Department of Inorganic Chemistry; Stanford Univ., CA (United States). Department of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
- Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Department of Inorganic Chemistry
- Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Department of Inorganic Chemistry ; Max Planck Institute for Chemical Energy Conversion, Mulheim (Germany)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1417300
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Topics in Catalysis
- Additional Journal Information:
- Journal Volume: 60; Journal Issue: 19-20; Journal ID: ISSN 1022-5528
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cu; Methanol synthesis catalyst; CO adsorption; DRIFTS
Citation Formats
Schumann, Julia, Kröhnert, Jutta, Frei, Elias, Schlögl, Robert, and Trunschke, Annette. IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer. United States: N. p., 2017.
Web. doi:10.1007/s11244-017-0850-9.
Schumann, Julia, Kröhnert, Jutta, Frei, Elias, Schlögl, Robert, & Trunschke, Annette. IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer. United States. doi:10.1007/s11244-017-0850-9.
Schumann, Julia, Kröhnert, Jutta, Frei, Elias, Schlögl, Robert, and Trunschke, Annette. Mon .
"IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer". United States. doi:10.1007/s11244-017-0850-9. https://www.osti.gov/servlets/purl/1417300.
@article{osti_1417300,
title = {IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer},
author = {Schumann, Julia and Kröhnert, Jutta and Frei, Elias and Schlögl, Robert and Trunschke, Annette},
abstractNote = {Carbon monoxide was applied as probe molecule to compare the surface of a ZnO-containing (Cu/ZnO:Al) and a ZnO-free (Cu/MgO) methanol synthesis catalyst (copper content 70 atomic %) after reduction in hydrogen at 523 K by DRIFT spectroscopy. Nano-structured, mainly metallic copper was detected on the surface of the Cu/MgO catalyst. In contrast, the high energy of the main peak in the spectrum of CO adsorbed on reduced Cu/ZnO:Al (2125 cm-1) proves that metallic copper is largely absent on the surface of this catalyst. The band is assigned to Znδ+–CO. The presence of not completely reduced Cuδ+–CO species cannot be excluded. The results are interpreted in terms of a partial coverage of the copper nano-particles in the Cu/ZnO:Al catalyst by a thin layer of metastable, defective zinc oxide. Minor contributions in the spectrum at 2090 and 2112 cm-1 due to nano-structured Cu0–CO and CO adsorbed on highly defective Cu0, respectively, indicate that the coverage of metallic copper is not complete.},
doi = {10.1007/s11244-017-0850-9},
journal = {Topics in Catalysis},
number = 19-20,
volume = 60,
place = {United States},
year = {2017},
month = {8}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 11 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Structural changes of the Cu surface of a Cu/ZnO/Al2O3 catalyst, resulting from oxidation and reduction, probed by CO infrared spectroscopy
journal, November 2000
- Sakakini, B. H.; Tabatabaei, J.; Watson, M. J.
- Journal of Molecular Catalysis A: Chemical, Vol. 162, Issue 1-2
In Situ Investigations of Structural Changes in Cu/ZnO Catalysts
journal, September 2000
- Grunwaldt, J. -D; Molenbroek, A. M.; Topsøe, N. -Y
- Journal of Catalysis, Vol. 194, Issue 2
A DRIFTS study of the morphology and surface adsorbate composition of an operating methanol synthesis catalyst
journal, January 1995
- Bailey, S.; Froment, G. F.; Snoeck, J. W.
- Catalysis Letters, Vol. 30, Issue 1-4
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions
journal, February 2015
- Lunkenbein, Thomas; Schumann, Julia; Behrens, Malte
- Angewandte Chemie International Edition, Vol. 54, Issue 15
In situ IR studies on the mechanism of methanol synthesis over an ultrafine Cu/ZnO/Al2O3 catalyst
journal, July 1998
- Sun, Qi; Liu, Chong-Wei; Pan, Wei
- Applied Catalysis A: General, Vol. 171, Issue 2
Quantitative effects of an absorbing matrix on near-infrared diffuse reflectance spectra
journal, November 1988
- Olinger, Jill M.; Griffiths, Peter R.
- Analytical Chemistry, Vol. 60, Issue 21
Principles and Techniques of Diffuse-Reflectance Spectroscopy
journal, July 1963
- Kortüm, G.; Braun, W.; Herzog, G.
- Angewandte Chemie International Edition in English, Vol. 2, Issue 7
Characterization of vacant coordination sites of cations on the surfaces of oxides and zeolites using infrared spectroscopy of adsorbed probe molecules
journal, June 2009
- Hadjiivanov, K.; Knözinger, H.
- Surface Science, Vol. 603, Issue 10-12
Carbon Monoxide-Induced Dynamic Metal-Surface Nanostructuring
journal, July 2014
- Carenco, Sophie
- Chemistry - A European Journal, Vol. 20, Issue 34
Infrared spectroscopy of chemisorbed carbon monoxide on copper
journal, December 1975
- Pritchard, J.; Catterick, T.; Gupta, R. K.
- Surface Science, Vol. 53, Issue 1
Carbon monoxide MgO from dispersed solids to single crystals: a review and new advances
journal, October 2004
- Spoto, G.; Gribov, E. N.; Ricchiardi, G.
- Progress in Surface Science, Vol. 76, Issue 3-5
Counting of Oxygen Defects versus Metal Surface Sites in Methanol Synthesis Catalysts by Different Probe Molecules
journal, May 2014
- Fichtl, Matthias B.; Schumann, Julia; Kasatkin, Igor
- Angewandte Chemie International Edition, Vol. 53, Issue 27
Evidence for the migration of ZnOx in a Cu/ZnO methanol synthesis catalyst
journal, January 1994
- Kanai, Y.; Watanabe, T.; Fujitani, T.
- Catalysis Letters, Vol. 27, Issue 1-2
Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper: Participants and Spectators
journal, November 2015
- Yang, Yong; Mei, Donghai; Peden, Charles H. F.
- ACS Catalysis, Vol. 5, Issue 12
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts
journal, March 2015
- Studt, Felix; Behrens, Malte; Kunkes, Edward L.
- ChemCatChem, Vol. 7, Issue 7
High-Pressure CO Adsorption on Cu-Based Catalysts: Zn-Induced Formation of Strongly Bound CO Monitored by ATR-IR Spectroscopy
journal, April 2011
- Liu, Zhimin; Rittermeier, André; Becker, Michael
- Langmuir, Vol. 27, Issue 8
Spectroscopic evidence for adsorption sites located at Cu/ZnO interfaces
journal, January 1995
- Bailie, Julian E.; Rochester, Colin H.; Millar, Graeme J.
- Catalysis Letters, Vol. 31, Issue 4
Chemical Activity of Thin Oxide Layers: Strong Interactions with the Support Yield a New Thin-Film Phase of ZnO
journal, September 2013
- Schott, Vadim; Oberhofer, Harald; Birkner, Alexander
- Angewandte Chemie International Edition, Vol. 52, Issue 45
New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions
journal, January 2014
- Zaera, Francisco
- Chem. Soc. Rev., Vol. 43, Issue 22
Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials’ Interface in Selective Hydrogenation of CO2 to CH3OH
journal, January 2011
- Liao, Fenglin; Huang, Yaqun; Ge, Junwei
- Angewandte Chemie International Edition, Vol. 50, Issue 9
Adsorption of carbon monoxide on copper Infrared absorption spectra and thermodesorption
journal, April 1965
- Smith, A.
- Journal of Catalysis, Vol. 4, Issue 2
Probing the surfaces of heterogeneous catalysts by in situ IR spectroscopy
journal, January 2010
- Lamberti, Carlo; Zecchina, Adriano; Groppo, Elena
- Chemical Society Reviews, Vol. 39, Issue 12
Synthesis and Characterisation of a Highly Active Cu/ZnO:Al Catalyst
journal, August 2014
- Schumann, Julia; Lunkenbein, Thomas; Tarasov, Andrey
- ChemCatChem, Vol. 6, Issue 10
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
journal, April 2012
- Behrens, M.; Studt, F.; Kasatkin, I.
- Science, Vol. 336, Issue 6083, p. 893-897
An infrared spectroscopic study of CO on Cu(111): The linear, bridging and physisorbed species
journal, June 1985
- Hayden, B. E.; Kretzschmar, K.; Bradshaw, A. M.
- Surface Science, Vol. 155, Issue 2-3
Reverse water-gas shift reaction at the Cu/ZnO interface: Influence of the Cu/Zn ratio on structure-activity correlations
journal, October 2016
- Álvarez Galván, Consuelo; Schumann, Julia; Behrens, Malte
- Applied Catalysis B: Environmental, Vol. 195
Bridging the Time Gap: A Copper/Zinc Oxide/Aluminum Oxide Catalyst for Methanol Synthesis Studied under Industrially Relevant Conditions and Time Scales
journal, September 2016
- Lunkenbein, Thomas; Girgsdies, Frank; Kandemir, Timur
- Angewandte Chemie International Edition, Vol. 55, Issue 41
Operando Synchrotron X-ray Powder Diffraction and Modulated-Excitation Infrared Spectroscopy Elucidate the CO 2 Promotion on a Commercial Methanol Synthesis Catalyst
journal, July 2016
- Martin, Oliver; Mondelli, Cecilia; Cervellino, Antonio
- Angewandte Chemie International Edition, Vol. 55, Issue 37
Quantitative Analysis of Adsorbate Concentrations by Diffuse Reflectance FT-IR
journal, May 2007
- Sirita, Jinda; Phanichphant, Sukon; Meunier, Frederic C.
- Analytical Chemistry, Vol. 79, Issue 10
The coverage-dependent adsorption of carbon monoxide on hydrogen-reduced copper catalysts: the combined application of microcalorimetry, temperature-programmed desorption and FTIR spectroscopy
journal, August 2005
- Naumann d’Alnoncourt, R.; Bergmann, M.; Strunk, J.
- Thermochimica Acta, Vol. 434, Issue 1-2
FTIR studies of dynamic surface structural changes in Cu-based methanol synthesis catalysts
journal, May 1999
- Topsøe, N.
- Journal of Molecular Catalysis A: Chemical, Vol. 141, Issue 1-3
Interactions of CO molecules adsorbed on Cu(111)
journal, January 1979
- Hollins, P.; Pritchard, J.
- Surface Science, Vol. 89, Issue 1-3
The influence of strongly reducing conditions on strong metal–support interactions in Cu/ZnO catalysts used for methanol synthesis
journal, January 2006
- Naumann d’Alnoncourt, R.; Xia, X.; Strunk, J.
- Physical Chemistry Chemical Physics, Vol. 8, Issue 13
Infrared study of CO adsorption on reduced and oxidised silica-supported copper catalysts
journal, January 1991
- Millar, Graeme J.; Rochester, Colin H.; Waugh, Kenneth C.
- Journal of the Chemical Society, Faraday Transactions, Vol. 87, Issue 9
The Role of the Oxide Component in the Development of Copper Composite Catalysts for Methanol Synthesis
journal, May 2013
- Zander, Stefan; Kunkes, Edward L.; Schuster, Manfred E.
- Angewandte Chemie International Edition, Vol. 52, Issue 25
Dynamic Behavior of the Surface Structure of Cu/ZnO/SiO2 Catalysts
journal, August 2002
- Jansen, W.
- Journal of Catalysis, Vol. 210, Issue 1
Probing zeolites by vibrational spectroscopies
journal, January 2015
- Bordiga, Silvia; Lamberti, Carlo; Bonino, Francesca
- Chemical Society Reviews, Vol. 44, Issue 20
Infrared Absorption Spectroscopy of Adsorbed CO: New Applications in Nanocatalysis for an Old Approach
journal, July 2012
- Zaera, Francisco
- ChemCatChem, Vol. 4, Issue 10
The synergy between Cu and ZnO in methanol synthesis catalysts
journal, January 1996
- Kanai, Y.; Watanabe, T.; Fujitani, T.
- Catalysis Letters, Vol. 38, Issue 3-4
Works referencing / citing this record:
Highly Selective Silica‐supported Copper Catalysts Derived from Copper Phyllosilicates in the Hydrogenation of Adipic Acid to 1,6‐hexanediol
journal, November 2018
- Jiang, Jia‐Wei; Tu, Cheng‐Chieh; Chen, Chao‐Huang
- ChemCatChem, Vol. 10, Issue 23
H 2 Adsorption on Wurtzite ZnO and on ZnO/M(111) (M=Cu, Ag and Au) Bilayer Films
journal, May 2019
- Thang, Ho Viet; Pacchioni, Gianfranco
- ChemNanoMat, Vol. 5, Issue 7
Mapping Support Interactions in Copper Catalysts
journal, February 2019
- Chatterjee, Rishika; Kuld, Sebastian; van den Berg, Roy
- Topics in Catalysis, Vol. 62, Issue 7-11
2D oxides on metal materials: concepts, status, and perspectives
journal, January 2019
- Barcaro, Giovanni; Fortunelli, Alessandro
- Physical Chemistry Chemical Physics, Vol. 21, Issue 22
One-pot direct conversion of levulinic acid into high-yield valeric acid over a highly stable bimetallic Nb-Cu/Zr-doped porous silica catalyst
journal, January 2020
- Karanwal, Neha; Verma, Deepak; Butolia, Paresh
- Green Chemistry, Vol. 22, Issue 3
Growth and structural studies of In/Au(111) alloys and InO x /Au(111) inverse oxide/metal model catalysts
journal, February 2020
- Kang, Jindong; Mahapatra, Mausumi; Rui, Ning
- The Journal of Chemical Physics, Vol. 152, Issue 5
Hydroxylation of ZnO/Cu(1 1 1) inverse catalysts under ambient water vapor and the water–gas shift reaction
journal, August 2019
- Orozco, Ivan; Huang, Erwei; Gutiérrez, Ramón A.
- Journal of Physics D: Applied Physics, Vol. 52, Issue 45