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Title: 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:
ORCiD logo [1];  [2]; ORCiD logo [1];  [1];  [3];  [1];  [1];  [3];  [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
  2. Central Univ. of Venezuela, Caracas (Venezuela). Faculty of Science; Zoneca-CENEX, R&D Lab., Monterrey (Mexico)
  3. 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) (SC-22)
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. 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., 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. doi: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 = {2017},
month = {8}
}

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Works referencing / citing this record:

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
  • DOI: 10.1039/c9cy00632j

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
  • DOI: 10.1039/c9cy00632j