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}
}
Web of Science
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