Hydrogenation of CO2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis
Abstract
The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θoxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making the supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO2 hydrogenation reaction. However, reaction with CO2 oxidized the zinc, enhancing its stability over the copper substrates.
- Authors:
-
[1];
[1];
[1];
[1]
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
- Central Univ. of Venezuela, Caracas (Venezuela). Faculty of Science; Zoneca-CENEX, R&D Lab., Monterrey (Mexico)
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II) and Photon Sciences Division
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1430850
- Report Number(s):
- BNL-203370-2018-JAAM
Journal ID: ISSN 1520-6106; TRN: US1802922
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 2; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE
Citation Formats
Palomino, Robert M., Ramirez, Pedro J., Liu, Zongyuan, Hamlyn, Rebecca, Waluyo, Iradwikanari, Mahapatra, Mausumi, Orozco, Ivan, Hunt, Adrian, Simonovis, Juan P., Senanayake, Sanjaya D., and Rodriguez, Jose A. Hydrogenation of CO2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcb.7b06901.
Palomino, Robert M., Ramirez, Pedro J., Liu, Zongyuan, Hamlyn, Rebecca, Waluyo, Iradwikanari, Mahapatra, Mausumi, Orozco, Ivan, Hunt, Adrian, Simonovis, Juan P., Senanayake, Sanjaya D., & Rodriguez, Jose A. Hydrogenation of CO2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis. United States. https://doi.org/10.1021/acs.jpcb.7b06901
Palomino, Robert M., Ramirez, Pedro J., Liu, Zongyuan, Hamlyn, Rebecca, Waluyo, Iradwikanari, Mahapatra, Mausumi, Orozco, Ivan, Hunt, Adrian, Simonovis, Juan P., Senanayake, Sanjaya D., and Rodriguez, Jose A. Mon .
"Hydrogenation of CO2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis". United States. https://doi.org/10.1021/acs.jpcb.7b06901. https://www.osti.gov/servlets/purl/1430850.
@article{osti_1430850,
title = {Hydrogenation of CO2 on ZnO/Cu(100) and ZnO/Cu(111) Catalysts: Role of Copper Structure and Metal–Oxide Interface in Methanol Synthesis},
author = {Palomino, Robert M. and Ramirez, Pedro J. and Liu, Zongyuan and Hamlyn, Rebecca and Waluyo, Iradwikanari and Mahapatra, Mausumi and Orozco, Ivan and Hunt, Adrian and Simonovis, Juan P. and Senanayake, Sanjaya D. and Rodriguez, Jose A.},
abstractNote = {The results of kinetic tests and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) show the important role played by a ZnO–copper interface in the generation of CO and the synthesis of methanol from CO2 hydrogenation. The deposition of nanoparticles of ZnO on Cu(100) and Cu(111), θoxi < 0.3 monolayer, produces highly active catalysts. The catalytic activity of these systems increases in the sequence: Cu(111) < Cu(100) < ZnO/Cu(111) < ZnO/Cu(100). The structure of the copper substrate influences the catalytic performance of a ZnO–copper interface. Furthermore, size and metal–oxide interactions affect the chemical and catalytic properties of the oxide making the supported nanoparticles different from bulk ZnO. The formation of a ZnO–copper interface favors the binding and conversion of CO2 into a formate intermediate that is stable on the catalyst surface up to temperatures above 500 K. Alloys of Zn with Cu(111) and Cu(100) were not stable at the elevated temperatures (500–600 K) used for the CO2 hydrogenation reaction. However, reaction with CO2 oxidized the zinc, enhancing its stability over the copper substrates.},
doi = {10.1021/acs.jpcb.7b06901},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 2,
volume = 122,
place = {United States},
year = {Mon Aug 21 00:00:00 EDT 2017},
month = {Mon Aug 21 00:00:00 EDT 2017}
}
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Works referenced in this record:
Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes
journal, January 2013
- Kondratenko, Evgenii V.; Mul, Guido; Baltrusaitis, Jonas
- Energy & Environmental Science, Vol. 6, Issue 11
Carbon Dioxide Recycling: Emerging Large-Scale Technologies with Industrial Potential
journal, September 2011
- Quadrelli, Elsje Alessandra; Centi, Gabriele; Duplan, Jean-Luc
- ChemSusChem, Vol. 4, Issue 9
The synthesis of higher alcohols using modified Cu/ZnO/Al2O3 catalysts
journal, May 1992
- Slaa, J. C.; van Ommen, J. G.; Ross, J. R. H.
- Catalysis Today, Vol. 15, Issue 1
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
Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts
journal, April 2015
- Schumann, Julia; Eichelbaum, Maik; Lunkenbein, Thomas
- ACS Catalysis, Vol. 5, Issue 6
Microstructural and Defect Analysis of Metal Nanoparticles in Functional Catalysts by Diffraction and Electron Microscopy: The Cu/ZnO Catalyst for Methanol Synthesis
journal, October 2013
- Kandemir, Timur; Kasatkin, Igor; Girgsdies, Frank
- Topics in Catalysis, Vol. 57, Issue 1-4
Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts
journal, March 2017
- Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G.
- Science, Vol. 355, Issue 6331
Hydrogenation of CO 2 to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO 2
journal, October 2015
- Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J.
- ACS Catalysis, Vol. 5, Issue 11
Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄)
journal, January 2010
- Yang, Yixiong; Evans, Jaime; Rodriguez, Jose A.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 33
Activity and Selectivity Trends in Synthesis Gas Conversion to Higher Alcohols
journal, October 2013
- Medford, Andrew J.; Lausche, Adam C.; Abild-Pedersen, Frank
- Topics in Catalysis, Vol. 57, Issue 1-4
Dissociative Carbon Dioxide Adsorption and Morphological Changes on Cu(100) and Cu(111) at Ambient Pressures
journal, June 2016
- Eren, Baran; Weatherup, Robert S.; Liakakos, Nikos
- Journal of the American Chemical Society, Vol. 138, Issue 26
Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity
journal, July 1996
- Yoshihara, Jun; Campbell, Charles T.
- Journal of Catalysis, Vol. 161, Issue 2
Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2
journal, January 1994
- Rasmussen, P. B.; Holmblad, P. M.; Askgaard, T.
- Catalysis Letters, Vol. 26, Issue 3-4
Methanol synthesis on a Cu(100) catalyst
journal, January 1991
- Szanyi, J�nos; Goodman, D. Wayne
- Catalysis Letters, Vol. 10, Issue 5-6
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
journal, July 2014
- Graciani, J.; Mudiyanselage, K.; Xu, F.
- Science, Vol. 345, Issue 6196
New In-Situ and Operando Facilities for Catalysis Science at NSLS-II: The Deployment of Real-Time, Chemical, and Structure-Sensitive X-ray Probes
journal, March 2017
- Palomino, Robert M.; Stavitski, Eli; Waluyo, Iradwikanari
- Synchrotron Radiation News, Vol. 30, Issue 2
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
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis
journal, May 2016
- Kuld, S.; Thorhauge, M.; Falsig, H.
- Science, Vol. 352, Issue 6288
Reactivity of Ultra-Thin ZnO Films Supported by Ag(111) and Cu(111): A Comparison to ZnO/Pt(111)
journal, February 2014
- Pan, Q.; Liu, B. H.; McBriarty, M. E.
- Catalysis Letters, Vol. 144, Issue 4
Auger and direct electron spectra in X-ray photoelectron studies of zinc, zinc oxide, gallium and gallium oxide
journal, January 1973
- Schön, Gunnar
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 2, Issue 1
Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties
journal, January 1997
- Campbell, Charles T.
- Surface Science Reports, Vol. 27, Issue 1-3
Surface studies of supported model catalysts
journal, January 1998
- Henry, Claude R.
- Surface Science Reports, Vol. 31, Issue 7-8
Inverse Oxide/Metal Catalysts in Fundamental Studies and Practical Applications: A Perspective of Recent Developments
journal, June 2016
- Rodriguez, José A.; Liu, Ping; Graciani, Jesús
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
Photoelectron spectroscopy under ambient pressure and temperature conditions
journal, March 2009
- Frank Ogletree, D.; Bluhm, Hendrik; Hebenstreit, Eleonore D.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2
Ambient pressure photoelectron spectroscopy: A new tool for surface science and nanotechnology
journal, April 2008
- Salmeron, M.; Schlogl, R.
- Surface Science Reports, Vol. 63, Issue 4
Identification of 5–7 Defects in a Copper Oxide Surface
journal, August 2011
- Yang, Fan; Choi, YongMan; Liu, Ping
- Journal of the American Chemical Society, Vol. 133, Issue 30
Hydrogenation of CO 2 to Methanol on CeO x /Cu(111) and ZnO/Cu(111) Catalysts: Role of the Metal–Oxide Interface and Importance of Ce 3+ Sites
journal, January 2016
- Senanayake, Sanjaya D.; Ramírez, Pedro J.; Waluyo, Iradwikanari
- The Journal of Physical Chemistry C, Vol. 120, Issue 3
Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy
journal, April 2013
- Mudiyanselage, Kumudu; Senanayake, Sanjaya D.; Feria, Leticia
- Angewandte Chemie International Edition, Vol. 52, Issue 19
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
Hydrogenation of CO2 to methanol and CO on Cu/ZnO/Al2O3: Is there a common intermediate or not?
journal, August 2015
- Kunkes, Edward L.; Studt, Felix; Abild-Pedersen, Frank
- Journal of Catalysis, Vol. 328
Works referencing / citing this record:
Morphology and chemical behavior of model CsO x /Cu 2 O/Cu(111) nanocatalysts for methanol synthesis: Reaction with CO 2 and H 2
journal, January 2020
- Hamlyn, Rebecca; Mahapatra, Mausumi; Orozco, Ivan
- The Journal of Chemical Physics, Vol. 152, Issue 4
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
Thermal reduction of ceria nanostructures on rhodium(111) and re-oxidation by CO 2
journal, January 2018
- Schaefer, Andreas; Hagman, Benjamin; Höcker, Jan
- Physical Chemistry Chemical Physics, Vol. 20, Issue 29
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
Methanol synthesis from CO2: a DFT investigation on Zn-promoted Cu catalyst
journal, December 2019
- Zheng, Huayan; Narkhede, Nilesh; Han, Linyi
- Research on Chemical Intermediates, Vol. 46, Issue 3
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
A mini review of in situ near-ambient pressure XPS studies on non-noble, late transition metal catalysts
journal, January 2019
- Zhong, Liping; Chen, Dingkai; Zafeiratos, Spyridon
- Catalysis Science & Technology, Vol. 9, Issue 15