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

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [2];  [3];  [2];  [3];  [4];  [4];  [3];  [2];  [2];  [5];  [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)
+ Show Author Affiliations

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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1440347
Alternate ID(s):
OSTI ID: 1460855
Report Number(s):
BNL--205724-2018-JAAM
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 24 Vol. 122; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (41)

Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO2 Catalysts for the Water–Gas Shift Reaction journal March 2008
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO 2 to CO journal May 2014
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
Surface Faceting and Reconstruction of Ceria Nanoparticles journal December 2016
Regulation of reaction intermediate by reactant in the water-gas shift reaction on CeO2, in relation to reactant-promoted mechanism journal August 1992
Industrial scale experience on steam reforming of CO 2 -rich gas journal April 2015
Morphology effect of nanostructure ceria on the Cu/CeO2 catalysts for synthesis of methanol from CO2 hydrogenation journal May 2017
Study of the origin of the deactivation of a Pt/CeO catalyst during reverse water gas shift (RWGS) reaction journal September 2004
Synthesis and analysis of CO2 adsorbents based on cerium oxide journal December 2014
Mechanisms and kinetics of CO 2 hydrogenation to value-added products: A detailed review on current status and future trends journal December 2017
Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces journal July 1998
Reaction of carboxylic acids on CeO2(111) and CeO2(100) journal September 1996
Development of ZnO/Al2O3 catalyst for reverse-water-gas-shift reaction of CAMERE (carbon dioxide hydrogenation to form methanol via a reverse-water-gas-shift reaction) process journal March 2001
Study of iron-promoted Cu/SiO2 catalyst on high temperature reverse water gas shift reaction journal January 2004
Reverse water gas shift reaction over Co-precipitated Ni-CeO2 catalysts journal February 2008
First-principles characterization of formate and carboxyl adsorption on stoichiometric CeO2(111) and CeO2(110) surfaces journal May 2013
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO 2 Hydrogenation Processes journal May 2017
Nanoshaped CuO/CeO 2 Materials: Effect of the Exposed Ceria Surfaces on Catalytic Activity in N 2 O Decomposition Reaction journal August 2015
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
Crystal Plane Effect of Ceria on Supported Copper Oxide Cluster Catalyst for CO Oxidation: Importance of Metal–Support Interaction journal January 2017
Ceria Catalysts at Nanoscale: How Do Crystal Shapes Shape Catalysis? journal June 2017
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
Carbon Dioxide Hydrogenation To Form Methanol via a Reverse-Water-Gas-Shift Reaction (the CAMERE Process) journal May 1999
Oxygen Vacancy Clusters Promoting Reducibility and Activity of Ceria Nanorods journal March 2009
Confinement of Ultrasmall Cu/ZnO x Nanoparticles in Metal–Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO 2 journal March 2017
Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO 2 Catalyst journal December 2004
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
Shape-Selective Synthesis and Oxygen Storage Behavior of Ceria Nanopolyhedra, Nanorods, and Nanocubes journal December 2005
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
Redox Pathways for HCOOH Decomposition over CeO 2 Surfaces journal June 2008
Mechanism of CO formation in reverse water–gas shift reaction over Cu/Al2O3 catalyst journal January 2000
Abrupt onset and prolongation of aragonite undersaturation events in the Southern Ocean journal November 2015
EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles journal January 2010
Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄) journal January 2010
Recent advances in catalytic hydrogenation of carbon dioxide journal January 2011
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
Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming journal January 2017
CO 2 conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO 2 conversion to liquid fuels journal January 2016
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
  • Li, Can; Sakata, Yoshihisa; Arai, Toru
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 4 https://doi.org/10.1039/f19898500929
journal January 1989
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

Cited By (7)

Combustion Synthesis of Non-Precious CuO-CeO2 Nanocrystalline Catalysts with Enhanced Catalytic Activity for Methane Oxidation journal March 2019
Bifunctional Synergy in CO Hydrogenation to Methanol with Supported Cu journal November 2019
Carboxyl intermediate formation via an in situ-generated metastable active site during water-gas shift catalysis journal September 2019
A mini review of in situ near-ambient pressure XPS studies on non-noble, late transition metal catalysts journal January 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
Insight into the structural characterization of pure and Zr-doped hydrothermally synthesized cerium oxide nanoparticles journal August 2019
CO2 Hydrogenation over Nanoceria-Supported Transition Metal Catalysts: Role of Ceria Morphology (Nanorods versus Nanocubes) and Active Phase Nature (Co versus Cu) journal December 2019

Figures / Tables (11)

Figure 1(p. 8)figure Figure 1
Figure 2(p. 8)figure Figure 2
Table 1(p. 9)table Table 1
Figure 3(p. 10)figure Figure 3
Figure 4(p. 11)figure Figure 4
Figure 5(p. 11)figure Figure 5
Figure 6(p. 13)figure Figure 6
Figure 7(p. 14)figure Figure 7
Table 2(p. 15)table Table 2
Figure 8(p. 16)figure Figure 8
Figure 9(p. 17)figure Figure 9

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