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

Title: In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity

Abstract

Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO2 nanocatalysts during the hydrogenation of CO2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO2-NR catalyst displayed the higher activity, which demonstrates that the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce4+ to Ce3+ transformation occurring. A more effective CO2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO2(110) terminations are probably the main reasons for the better performance of the Cu/CeO2-NR catalyst in the RWGS reaction.

Authors:
 [1];  [2];  [2];  [3];  [2];  [3];  [4];  [4];  [3];  [2];  [2];  [5]; ORCiD logo [6]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Peking Univ., Beijing (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. State Univ. of New York at Stony Brook, Stony Brook, NY (United States)
  4. Instituto de Catalisis y Petroleoquimica, Madrid (Spain)
  5. Peking Univ., Beijing (China)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States); State Univ. of New York at Stony Brook, Stony Brook, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1440347
Report Number(s):
BNL-205724-2018-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 24; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Lin, Lili, Yao, Siyu, Liu, Zongyuan, Zhang, Feng, Na, Li, Vovchok, Dimitriy, Martinez-Arias, Arturo, Castaneda, Rafael, Lin, Jin Ying, Senanayake, Sanjaya D., Su, Dong, Ma, Ding, and Rodriguez, Jose A. In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b03596.
Lin, Lili, Yao, Siyu, Liu, Zongyuan, Zhang, Feng, Na, Li, Vovchok, Dimitriy, Martinez-Arias, Arturo, Castaneda, Rafael, Lin, Jin Ying, Senanayake, Sanjaya D., Su, Dong, Ma, Ding, & Rodriguez, Jose A. In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity. United States. https://doi.org/10.1021/acs.jpcc.8b03596
Lin, Lili, Yao, Siyu, Liu, Zongyuan, Zhang, Feng, Na, Li, Vovchok, Dimitriy, Martinez-Arias, Arturo, Castaneda, Rafael, Lin, Jin Ying, Senanayake, Sanjaya D., Su, Dong, Ma, Ding, and Rodriguez, Jose A. Mon . "In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity". United States. https://doi.org/10.1021/acs.jpcc.8b03596. https://www.osti.gov/servlets/purl/1440347.
@article{osti_1440347,
title = {In-situ Characterization of Cu/CeO2 Nanocatalysts during CO2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity},
author = {Lin, Lili and Yao, Siyu and Liu, Zongyuan and Zhang, Feng and Na, Li and Vovchok, Dimitriy and Martinez-Arias, Arturo and Castaneda, Rafael and Lin, Jin Ying and Senanayake, Sanjaya D. and Su, Dong and Ma, Ding and Rodriguez, Jose A.},
abstractNote = {Here, a combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to carry out an in-situ characterization of Cu/CeO2 nanocatalysts during the hydrogenation of CO2. Morphological effects of the ceria supports on the catalytic performances were investigated by examining the behavior of copper/ceria-nanorods (NR) and nanospheres (NS). At atmospheric pressures, the hydrogenation of CO2 on the copper-ceria catalysts produced mainly CO through the reverse-water gas shift reaction (RWGS) and a negligible amount of methanol. The Cu/CeO2-NR catalyst displayed the higher activity, which demonstrates that the RWGS is a structure sensitive reaction. In-situ TR-XRD and AP-XPS characterization showed significant changes in the chemical state of the catalysts under reaction conditions with the copper being fully reduced and a partial Ce4+ to Ce3+ transformation occurring. A more effective CO2 dissociative activation at high temperature and a preferential formation of active bidentate carbonate and formate intermediates over CeO2(110) terminations are probably the main reasons for the better performance of the Cu/CeO2-NR catalyst in the RWGS reaction.},
doi = {10.1021/acs.jpcc.8b03596},
journal = {Journal of Physical Chemistry. C},
number = 24,
volume = 122,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 128 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Representative TEM and HR-TEM images of nanostructured Cu/CeO2 catalysts. (a) Cu/CeO2-nanorods, (b) Cu/CeO2-nanospheres, and (c) Cu/CeO2-nanocubes.

Save / Share:

Works referenced in this record:

Abrupt onset and prolongation of aragonite undersaturation events in the Southern Ocean
journal, November 2015

  • Hauri, Claudine; Friedrich, Tobias; Timmermann, Axel
  • Nature Climate Change, Vol. 6, Issue 2
  • DOI: 10.1038/nclimate2844

Recent advances in catalytic hydrogenation of carbon dioxide
journal, January 2011

  • Wang, Wei; Wang, Shengping; Ma, Xinbin
  • Chemical Society Reviews, Vol. 40, Issue 7
  • DOI: 10.1039/c1cs15008a

Industrial scale experience on steam reforming of CO 2 -rich gas
journal, April 2015


Confinement of Ultrasmall Cu/ZnO x Nanoparticles in Metal–Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO 2
journal, March 2017

  • An, Bing; Zhang, Jingzheng; Cheng, Kang
  • Journal of the American Chemical Society, Vol. 139, Issue 10
  • DOI: 10.1021/jacs.7b00058

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO 2 Hydrogenation Processes
journal, May 2017


Mechanisms and kinetics of CO 2 hydrogenation to value-added products: A detailed review on current status and future trends
journal, December 2017

  • Saeidi, Samrand; Najari, Sara; Fazlollahi, Farhad
  • Renewable and Sustainable Energy Reviews, Vol. 80
  • DOI: 10.1016/j.rser.2017.05.204

Carbon Dioxide Hydrogenation To Form Methanol via a Reverse-Water-Gas-Shift Reaction (the CAMERE Process)
journal, May 1999

  • Joo, Oh-Shim; Jung, Kwang-Deog; Moon, Il
  • Industrial & Engineering Chemistry Research, Vol. 38, Issue 5
  • DOI: 10.1021/ie9806848

Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO
journal, May 2014

  • Porosoff, Marc D.; Yang, Xiaofang; Boscoboinik, J. Anibal
  • Angewandte Chemie International Edition, Vol. 53, Issue 26
  • DOI: 10.1002/anie.201404109

Study of the origin of the deactivation of a Pt/CeO catalyst during reverse water gas shift (RWGS) reaction
journal, September 2004


Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO 2 Catalyst
journal, December 2004

  • Goguet, Alexandre; Meunier, Frederic C.; Tibiletti, Daniele
  • The Journal of Physical Chemistry B, Vol. 108, Issue 52
  • DOI: 10.1021/jp047242w

In Situ Studies of the Active Sites for the Water Gas Shift Reaction over Cu−CeO 2 Catalysts:  Complex Interaction between Metallic Copper and Oxygen Vacancies of Ceria
journal, January 2006

  • Wang, Xianqin; Rodriguez, José A.; Hanson, Jonathan C.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 1
  • DOI: 10.1021/jp055467g

Oxygen Vacancy Clusters Promoting Reducibility and Activity of Ceria Nanorods
journal, March 2009

  • Liu, Xiangwen; Zhou, Kebin; Wang, Lei
  • Journal of the American Chemical Society, Vol. 131, Issue 9
  • DOI: 10.1021/ja808433d

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

Nanoshaped CuO/CeO 2 Materials: Effect of the Exposed Ceria Surfaces on Catalytic Activity in N 2 O Decomposition Reaction
journal, August 2015


Morphology effect of nanostructure ceria on the Cu/CeO2 catalysts for synthesis of methanol from CO2 hydrogenation
journal, May 2017


Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO2 Catalysts for the Water–Gas Shift Reaction
journal, March 2008


Ceria Catalysts at Nanoscale: How Do Crystal Shapes Shape Catalysis?
journal, June 2017


Redox Pathways for HCOOH Decomposition over CeO 2 Surfaces
journal, June 2008

  • Senanayake, Sanjaya D.; Mullins, David R.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 26
  • DOI: 10.1021/jp8016425

Highly Dispersed Copper over β-Mo 2 C as an Efficient and Stable Catalyst for the Reverse Water Gas Shift (RWGS) Reaction
journal, December 2016


Mechanism of CO formation in reverse water–gas shift reaction over Cu/Al2O3 catalyst
journal, January 2000

  • Chen, Ching‐Shiun; Cheng, Wu‐Hsun; Lin, Shou‐Shiun
  • Catalysis Letters, Vol. 68, Issue 1/2, p. 45-48
  • DOI: 10.1023/A:1019071117449

Surface Faceting and Reconstruction of Ceria Nanoparticles
journal, December 2016

  • Yang, Chengwu; Yu, Xiaojuan; Heißler, Stefan
  • Angewandte Chemie International Edition, Vol. 56, Issue 1
  • DOI: 10.1002/anie.201609179

Shape-Selective Synthesis and Oxygen Storage Behavior of Ceria Nanopolyhedra, Nanorods, and Nanocubes
journal, December 2005

  • Mai, Hao-Xin; Sun, Ling-Dong; Zhang, Ya-Wen
  • The Journal of Physical Chemistry B, Vol. 109, Issue 51
  • DOI: 10.1021/jp055584b

EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles
journal, January 2010

  • Beale, Andrew M.; Weckhuysen, Bert M.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 21
  • DOI: 10.1039/b925206a

Dry Reforming of Methane on a Highly-Active Ni-CeO 2 Catalyst: Effects of Metal-Support Interactions on C−H Bond Breaking
journal, May 2016

  • Liu, Zongyuan; Grinter, David C.; Lustemberg, Pablo G.
  • Angewandte Chemie International Edition, Vol. 55, Issue 26
  • DOI: 10.1002/anie.201602489

Carbon monoxide and carbon dioxide adsorption on cerium oxide studied by Fourier-transform infrared spectroscopy. Part 1.—Formation of carbonate species on dehydroxylated CeO2, at room temperature
journal, January 1989

  • Li, Can; Sakata, Yoshihisa; Arai, Toru
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 4
  • DOI: 10.1039/f19898500929

Synthesis and analysis of CO2 adsorbents based on cerium oxide
journal, December 2014


Reassignment of the Vibrational Spectra of Carbonates, Formates, and Related Surface Species on Ceria: A Combined Density Functional and Infrared Spectroscopy Investigation
journal, November 2011

  • Vayssilov, Georgi N.; Mihaylov, Mihail; Petkov, Petko St.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 47
  • DOI: 10.1021/jp208050a

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
  • DOI: 10.1039/c001484b

The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
journal, April 2012


Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts
journal, March 2017


Works referencing / citing this record:

Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift catalysis
journal, September 2019

  • Nelson, Nicholas C.; Nguyen, Manh-Thuong; Glezakou, Vassiliki-Alexandra
  • Nature Catalysis, Vol. 2, Issue 10
  • DOI: 10.1038/s41929-019-0343-2

Insight into the structural characterization of pure and Zr-doped hydrothermally synthesized cerium oxide nanoparticles
journal, August 2019

  • Mazhar, Muhammad Ehsan; Bakhtawar, Samia; Manzoor Rana, Anwar
  • Materials Research Express, Vol. 6, Issue 10
  • DOI: 10.1088/2053-1591/ab0f5f

Bifunctional Synergy in CO Hydrogenation to Methanol with Supported Cu
journal, November 2019


Conversion of CO 2 on a highly active and stable Cu/FeO x /CeO 2 catalyst: tuning catalytic performance by oxide-oxide interactions
journal, January 2019

  • Lin, Lili; Yao, Siyu; Rui, Ning
  • Catalysis Science & Technology, Vol. 9, Issue 14
  • DOI: 10.1039/c9cy00722a

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