DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

Abstract

We have studied the catalytic carbon monoxide (CO) oxidation (CO+0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5wt% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray Diffraction (XRD), X-ray Absorption Fine Structure (XAFS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including Transmission Electron Microscopy (TEM), the local catalyst morphology and structure was also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggests that a surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Bothmore » in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [1];  [3];  [1];  [1];  [4];  [3];  [1];  [5]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. City College of New York, NY (United States)
  3. Stony Brook Univ., NY (United States)
  4. Yeshiva Univ., New York, NY (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1329786
Alternate Identifier(s):
OSTI ID: 1359911
Report Number(s):
BNL-112732-2016-JA
Journal ID: ISSN 0039-6028; R&D Project: CO009; KC0302010
Grant/Contract Number:  
SC00112704; SC0012704; FG02-03ER15476; SC0012335
Resource Type:
Accepted Manuscript
Journal Name:
Surface Science
Additional Journal Information:
Journal Volume: 652; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Senanayake, S. D., Pappoe, N. A., Nguyen-Phan, T. -D., Luo, S., Li, Y., Xu, W., Liu, Z., Mudiyanselage, K., Johnston-Peck, A. C., Frenkel, A. I., Heckler, I., Stacchiola, D., and Rodriguez, J. A. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts. United States: N. p., 2016. Web. doi:10.1016/j.susc.2016.02.014.
Senanayake, S. D., Pappoe, N. A., Nguyen-Phan, T. -D., Luo, S., Li, Y., Xu, W., Liu, Z., Mudiyanselage, K., Johnston-Peck, A. C., Frenkel, A. I., Heckler, I., Stacchiola, D., & Rodriguez, J. A. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts. United States. https://doi.org/10.1016/j.susc.2016.02.014
Senanayake, S. D., Pappoe, N. A., Nguyen-Phan, T. -D., Luo, S., Li, Y., Xu, W., Liu, Z., Mudiyanselage, K., Johnston-Peck, A. C., Frenkel, A. I., Heckler, I., Stacchiola, D., and Rodriguez, J. A. Sat . "Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts". United States. https://doi.org/10.1016/j.susc.2016.02.014. https://www.osti.gov/servlets/purl/1329786.
@article{osti_1329786,
title = {Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts},
author = {Senanayake, S. D. and Pappoe, N. A. and Nguyen-Phan, T. -D. and Luo, S. and Li, Y. and Xu, W. and Liu, Z. and Mudiyanselage, K. and Johnston-Peck, A. C. and Frenkel, A. I. and Heckler, I. and Stacchiola, D. and Rodriguez, J. A.},
abstractNote = {We have studied the catalytic carbon monoxide (CO) oxidation (CO+0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5wt% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray Diffraction (XRD), X-ray Absorption Fine Structure (XAFS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including Transmission Electron Microscopy (TEM), the local catalyst morphology and structure was also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggests that a surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.},
doi = {10.1016/j.susc.2016.02.014},
journal = {Surface Science},
number = ,
volume = 652,
place = {United States},
year = {Sat Oct 01 00:00:00 EDT 2016},
month = {Sat Oct 01 00:00:00 EDT 2016}
}

Journal Article:

Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Mechanism of CO Oxidation on Pt(111) in Alkaline Media
journal, May 2006

  • Spendelow, J. S.; Goodpaster, J. D.; Kenis, P. J. A.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 19
  • DOI: 10.1021/jp060100c

Spectroscopic Observation of Dual Catalytic Sites During Oxidation of CO on a Au/TiO2 Catalyst
journal, August 2011


Low-Temperature Catalytic H2 Oxidation over Au Nanoparticle/TiO2 Dual Perimeter Sites
journal, May 2011

  • Green, Isabel Xiaoye; Tang, Wenjie; Neurock, Matthew
  • Angewandte Chemie International Edition, Vol. 50, Issue 43
  • DOI: 10.1002/anie.201101612

The CO oxidation mechanism and reactivity on PdZn alloys
journal, January 2013

  • Johnson, Ryan S.; DeLaRiva, Andrew; Ashbacher, Valerie
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 20
  • DOI: 10.1039/c3cp00126a

Titanium dioxide based high temperature carbon monoxide selective sensor
journal, February 2001


Investigation of catalytic oxidation of carbon monoxide over a Cu–Cr-oxide catalyst made by self-propagating high-temperature synthesis
journal, October 1998


Fundamental Studies of Well-Defined Surfaces of Mixed-Metal Oxides: Special Properties of MO x /TiO 2 (110) {M = V, Ru, Ce, or W}
journal, December 2012

  • Stacchiola, Darío J.; Senanayake, Sanjaya D.; Liu, Ping
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300316v

Nature of the Mixed-Oxide Interface in Ceria–Titania Catalysts: Clusters, Chains, and Nanoparticles
journal, July 2013

  • Johnston-Peck, Aaron C.; Senanayake, Sanjaya D.; Plata, José J.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 28
  • DOI: 10.1021/jp3125268

Stabilization of Catalytically Active Cu + Surface Sites on Titanium-Copper Mixed-Oxide Films
journal, April 2014

  • Baber, Ashleigh E.; Yang, Xiaofang; Kim, Hyun You
  • Angewandte Chemie International Edition, Vol. 53, Issue 21
  • DOI: 10.1002/anie.201402435

Tuning the Properties of Copper-Based Catalysts Based on Molecular in Situ Studies of Model Systems
journal, June 2015


How to stabilize highly active Cu+ cations in a mixed-oxide catalyst
journal, April 2016


Direct Epoxidation of Propylene over Stabilized Cu + Surface Sites on Titanium-Modified Cu 2 O
journal, July 2015

  • Yang, Xiaofang; Kattel, Shyam; Xiong, Ke
  • Angewandte Chemie International Edition, Vol. 54, Issue 41
  • DOI: 10.1002/anie.201504538

Complex Catalytic Behaviors of CuTiO x Mixed-Oxide during CO Oxidation
journal, September 2015


Combining X-ray Absorption and X-ray Diffraction Techniques for in Situ Studies of Chemical Transformations in Heterogeneous Catalysis: Advantages and Limitations
journal, August 2011

  • Frenkel, A. I.; Wang, Q.; Marinkovic, N.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 36
  • DOI: 10.1021/jp205204e

Morphological effects of the nanostructured ceria support on the activity and stability of CuO/CeO 2 catalysts for the water-gas shift reaction
journal, January 2014

  • Yao, S. Y.; Xu, W. Q.; Johnston-Peck, A. C.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 32
  • DOI: 10.1039/C4CP02276A

Copper(I) and silver(I) carbonyls. To be or not to be nonclassical
journal, January 2000

  • Strauss, Steven H.
  • Journal of the Chemical Society, Dalton Transactions, Issue 1
  • DOI: 10.1039/a908459b

Unraveling the Dynamic Nature of a CuO/CeO 2 Catalyst for CO Oxidation in Operando : A Combined Study of XANES (Fluorescence) and DRIFTS
journal, April 2014

  • Yao, Siyu; Mudiyanselage, Kumudu; Xu, Wenqian
  • ACS Catalysis, Vol. 4, Issue 6
  • DOI: 10.1021/cs500148e

X-ray absorption edge determination of the oxidation state and coordination number of copper. Application to the type 3 site in Rhus vernicifera laccase and its reaction with oxygen
journal, October 1987

  • Kau, Lung Shan; Spira-Solomon, Darlene J.; Penner-Hahn, James E.
  • Journal of the American Chemical Society, Vol. 109, Issue 21
  • DOI: 10.1021/ja00255a032

X-ray absorption spectroscopic studies of the blue copper site: metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin
journal, January 1993

  • Shadle, Susan E.; Penner-Hahn, James E.; Schugar, Harvey J.
  • Journal of the American Chemical Society, Vol. 115, Issue 2
  • DOI: 10.1021/ja00055a057

Cu K-edge XANES of (La1-xSrx)2CuO4, YBa2Cu3Oy and related Cu oxides. valence, structure and final-state effects on 1s-4pπ and 1s-4pσ absorption
journal, July 1989


Number of relevant independent points in x-ray-absorption fine-structure spectra
journal, October 1993


Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010

  • Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 21
  • DOI: 10.1039/b926434e

Works referencing / citing this record:

Effect of Ce Doping on Catalytic Performance of Cu/TiO2 for CO Oxidation
journal, February 2020


The influence of support composition on the activity of Cu:Ce catalysts for selective catalytic reduction of NO by CO in the presence of excess oxygen
journal, January 2020

  • Gholami, Zahra; Luo, Guohua; Gholami, Fatemeh
  • New Journal of Chemistry, Vol. 44, Issue 3
  • DOI: 10.1039/c9nj04335g