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Title: Effects of Molecular and Electronic Structures in CoOx/CeO2 Catalysts on NO Reduction by CO

Abstract

Ceria-supported transition metal oxide (such as CoOx) catalysts are promising, more cost-effective candidates to replace platinum group metal catalysts in the NO reduction process. A series of CoOx (0.2–31.3 Co/nm2) catalysts supported on CeO2 were prepared by the incipient wetness impregnation method and were tested for NO reduction by CO reaction in this work. Various characterization techniques, including Brunauer–Emmett–Teller, Raman spectroscopy, powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were used to investigate the molecular and electronic structures of CoOx/CeO2 catalysts. It was observed that there are structural changes with varied Co loadings, such as (1) sub-monolayer: <2.3 Co/nm2, (2) monolayer: 2.3–2.7 Co/nm2, and (3) over-monolayer: >2.7 Co/nm2. The highest molar rate was observed at the 2.7 Co/nm2 sample. In the case of over-monolayer samples, such as 7.1 Co/nm2, the oxidation state of Co affected the catalytic activity. Using in situ XAS, an oxidation state change from Co3+ to Co2+ between 200 and 300 °C was identified. Catalyst deactivation was also affected by the change of Co oxidation states from the fresh sample (Co3+) to the used sample (Co3+/Co2+). N2O formation and decomposition were affected by the reaction temperature in a two-stepmore » procedure, where NO converts into N2: (1) NO → N2O and (2) N2O → N2. N2 selectivity monotonically increased with an increasing reaction temperature between 200 and 400 °C. Furthermore, the results provided several structure–property relationships and a possible reaction mechanism for NO reduction by CO reaction over CoOx/CeO2 catalysts.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Stony Brook Univ., Stony Brook, NY (United States)
  2. Seoul National Univ., Seoul (Republic of Korea)
  3. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, 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:
1508522
Report Number(s):
BNL-211570-2019-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: 123; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION

Citation Formats

Zhang, Shuhao, Li, Yuanyuan, Huang, Jiahao, Lee, Jaeha, Kim, Do Heui, Frenkel, Anatoly I., and Kim, Taejin. Effects of Molecular and Electronic Structures in CoOx/CeO2 Catalysts on NO Reduction by CO. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.8b12442.
Zhang, Shuhao, Li, Yuanyuan, Huang, Jiahao, Lee, Jaeha, Kim, Do Heui, Frenkel, Anatoly I., & Kim, Taejin. Effects of Molecular and Electronic Structures in CoOx/CeO2 Catalysts on NO Reduction by CO. United States. https://doi.org/10.1021/acs.jpcc.8b12442
Zhang, Shuhao, Li, Yuanyuan, Huang, Jiahao, Lee, Jaeha, Kim, Do Heui, Frenkel, Anatoly I., and Kim, Taejin. Mon . "Effects of Molecular and Electronic Structures in CoOx/CeO2 Catalysts on NO Reduction by CO". United States. https://doi.org/10.1021/acs.jpcc.8b12442. https://www.osti.gov/servlets/purl/1508522.
@article{osti_1508522,
title = {Effects of Molecular and Electronic Structures in CoOx/CeO2 Catalysts on NO Reduction by CO},
author = {Zhang, Shuhao and Li, Yuanyuan and Huang, Jiahao and Lee, Jaeha and Kim, Do Heui and Frenkel, Anatoly I. and Kim, Taejin},
abstractNote = {Ceria-supported transition metal oxide (such as CoOx) catalysts are promising, more cost-effective candidates to replace platinum group metal catalysts in the NO reduction process. A series of CoOx (0.2–31.3 Co/nm2) catalysts supported on CeO2 were prepared by the incipient wetness impregnation method and were tested for NO reduction by CO reaction in this work. Various characterization techniques, including Brunauer–Emmett–Teller, Raman spectroscopy, powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were used to investigate the molecular and electronic structures of CoOx/CeO2 catalysts. It was observed that there are structural changes with varied Co loadings, such as (1) sub-monolayer: <2.3 Co/nm2, (2) monolayer: 2.3–2.7 Co/nm2, and (3) over-monolayer: >2.7 Co/nm2. The highest molar rate was observed at the 2.7 Co/nm2 sample. In the case of over-monolayer samples, such as 7.1 Co/nm2, the oxidation state of Co affected the catalytic activity. Using in situ XAS, an oxidation state change from Co3+ to Co2+ between 200 and 300 °C was identified. Catalyst deactivation was also affected by the change of Co oxidation states from the fresh sample (Co3+) to the used sample (Co3+/Co2+). N2O formation and decomposition were affected by the reaction temperature in a two-step procedure, where NO converts into N2: (1) NO → N2O and (2) N2O → N2. N2 selectivity monotonically increased with an increasing reaction temperature between 200 and 400 °C. Furthermore, the results provided several structure–property relationships and a possible reaction mechanism for NO reduction by CO reaction over CoOx/CeO2 catalysts.},
doi = {10.1021/acs.jpcc.8b12442},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 123,
place = {United States},
year = {2019},
month = {3}
}

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Works referenced in this record:

On the dry and mixed reforming of methane over Ni/Al2O3 – Influence of reaction variables on syngas production
journal, December 2016

  • Karemore, Ashvin L.; Vaidya, Prakash D.; Sinha, Renu
  • International Journal of Hydrogen Energy, Vol. 41, Issue 48
  • DOI: 10.1016/j.ijhydene.2016.09.038

Automotive exhaust catalysis
journal, May 2003


Rapidly Pulsed Reductants for Diesel NOx Reduction With Lean NOx Traps: Comparison of Alkanes and Alkenes as the Reducing Agent
journal, April 2017

  • Reihani, Amin; Patterson, Brent; Hoard, John
  • Journal of Engineering for Gas Turbines and Power, Vol. 139, Issue 10
  • DOI: 10.1115/1.4036295

Catalytic NOx Reduction in Net Oxidizing Exhaust Gas
conference, February 1990

  • Held, Wolfgang; König, Axel; Richter, Thomas
  • International Congress & Exposition, SAE Technical Paper Series
  • DOI: 10.4271/900496

NO x Storage-Reduction Catalysts for Gasoline Engines
journal, April 2004


Promotional effect of zirconium additives on Ti 0.8 Ce 0.2 O 2 for selective catalytic reduction of NO
journal, January 2012

  • Shen, Yuesong; Ma, Yifan; Zhu, Shemin
  • Catal. Sci. Technol., Vol. 2, Issue 3
  • DOI: 10.1039/C2CY00363E

Catalytic performance and hydrothermal durability of CeO2–V2O5–ZrO2/WO3–TiO2 based NH3-SCR catalysts
journal, January 2012

  • Wang, Xinquan; Shi, Anju; Duan, Yingfeng
  • Catalysis Science & Technology, Vol. 2, Issue 7
  • DOI: 10.1039/c2cy20140b

Catalyst Design Based on DFT Calculations: Metal Oxide Catalysts for Gas Phase NO Reduction
journal, June 2014

  • Du, Xuesen; Gao, Xiang; Hu, Wenshuo
  • The Journal of Physical Chemistry C, Vol. 118, Issue 25
  • DOI: 10.1021/jp502040y

Design of a “high-efficiency” NH3-SCR reactor for stationary applications. A kinetic study of NH3 oxidation and NH3-SCR over V-based catalysts
journal, December 2015


Impacts of niobia loading on active sites and surface acidity in NbO /CeO2–ZrO2 NH3–SCR catalysts
journal, December 2015


Selective catalytic reduction of NO with NH 3 over novel iron–tungsten mixed oxide catalyst in a broad temperature range
journal, January 2015

  • Li, Xiang; Li, Junhua; Peng, Yue
  • Catalysis Science & Technology, Vol. 5, Issue 9
  • DOI: 10.1039/C5CY00605H

Catalysis for NOx abatement
journal, November 2009


Selective reduction of nitric oxide over noble metals
journal, May 1980


Nitrous oxide formation during the reaction of simulated exhaust streams over rhodium, platinum and palladium catalysts
journal, June 1998


The new concept 3-way catalyst for automotive lean-burn engine: NOx storage and reduction catalyst
journal, January 1996


Catalytic removal of nitric oxide with hydrogen and carbon monoxide in the presence of excess oxygen
journal, November 1997


An overview of kinetic and spectroscopic investigations on three-way catalysts: mechanistic aspects of the CO+NO and CO+N2O reactions
journal, March 2005


Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI)
journal, July 2015


Effect of metal–support interaction on the selective hydrodeoxygenation of anisole to aromatics over Ni-based catalysts
journal, February 2014

  • Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A.
  • Applied Catalysis B: Environmental, Vol. 145
  • DOI: 10.1016/j.apcatb.2013.03.038

Strong metal-support interaction and alloying in Pd/ZnO catalysts for CO oxidation
journal, February 2016


Kinetics of the NO and CO Reaction over Platinum Catalysts
journal, January 1998


Pd-xMo/Al2O3 Catalysts for NO Reduction by CO
journal, July 1999

  • Schmal, Martin; Baldanza, M. A. S.; Vannice, M. Albert
  • Journal of Catalysis, Vol. 185, Issue 1
  • DOI: 10.1006/jcat.1999.2465

Monolayer Detection of Supported Fe and Co Oxides on Ceria To Establish Structure–Activity Relationships for Reduction of NO by CO
journal, April 2017

  • Peck, Torin C.; Reddy, Gunugunuri K.; Jones, Michael
  • The Journal of Physical Chemistry C, Vol. 121, Issue 15
  • DOI: 10.1021/acs.jpcc.7b00398

A DFT Study on CO Oxidation over Co3O4
journal, August 2002


Structural and morphological investigation of a cobalt catalyst supported on alumina-baria: effects of redox treatments on the activity in the NO reduction by CO
journal, September 2004


The influence of Mn-doped CeO2 on the activity of CuO/CeO2 in CO oxidation and NO + CO model reaction
journal, December 2016


Influence of supports on the activities of copper oxide species in the low-temperature NO+CO reaction
journal, April 2001


Redox behavior and catalytic properties of CuO/Ce0.8Zr0.2O2 catalysts
journal, March 2003


Cobalt(III)-Catalyzed Hydroarylation of Allenes via C–H Activation
journal, March 2017


The ordered mesoporous transition metal oxides for selective catalytic reduction of NOx at low temperature
journal, October 2015


Catalytic carbon monoxide oxidation over CoOx/CeO2 composite catalysts
journal, September 2003


Catalytic hydrogen production through WGS or steam reforming of alcohols over Cu, Ni and Co catalysts
journal, May 2016


Biogas to syngas conversion without carbonaceous deposits via the dry reforming reaction using transition metal catalysts
journal, September 2015


Bio-ethanol steam reforming for hydrogen production over Co3O4/CeO2 catalysts synthesized by one-step polymerization method
journal, February 2016

  • Carvalho, Flávio L. S.; Asencios, Yvan J. O.; Bellido, Jorge D. A.
  • Fuel Processing Technology, Vol. 142
  • DOI: 10.1016/j.fuproc.2015.10.010

A Co 3 O 4 –CeO 2 functionalized SBA-15 monolith with a three-dimensional framework improves NO x -assisted soot combustion
journal, January 2015

  • Yang, Qiongqiong; Gu, Fangna; Tang, Yufang
  • RSC Advances, Vol. 5, Issue 34
  • DOI: 10.1039/C4RA16832A

Enhanced CO Oxidation Rates at the Interface of Mesoporous Oxides and Pt Nanoparticles
journal, October 2013

  • An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan
  • Journal of the American Chemical Society, Vol. 135, Issue 44
  • DOI: 10.1021/ja4088743

On the Catalytic Activity of Co3O4 in Low-Temperature CO Oxidation
journal, October 2002


Core-shell type ceria zirconia support for platinum and rhodium three way catalysts
journal, March 2017


Selective catalytic reduction of NO by NH3 over a Ce/TiO2 catalyst
journal, March 2008


NO reduction by CO over CuO supported on CeO 2 -doped TiO 2 : the effect of the amount of a few CeO 2
journal, January 2015

  • Deng, Changshun; Li, Bin; Dong, Lihui
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 24
  • DOI: 10.1039/C5CP00745C

DRIFT Study of CuO–CeO 2 –TiO 2 Mixed Oxides for NO x Reduction with NH 3 at Low Temperatures
journal, May 2014

  • Chen, Lei; Si, Zhichun; Wu, Xiaodong
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 11
  • DOI: 10.1021/am5004969

A DFT study of the structural, electronic and optical properties of transition metal doped fluorite oxides: Ce0.75M0.25O2 (M=Fe, Co, Ni)
journal, April 2016


Surface and redox properties of cobalt–ceria binary oxides: On the effect of Co content and pretreatment conditions
journal, June 2015


DRIFTS study of photo-assisted catalytic CO + NO redox reaction over CuO/CeO2-TiO2
journal, December 2015


Structure and Electronic Properties of Solid Acids Based on Tungsten Oxide Nanostructures
journal, January 1999

  • Barton, David G.; Shtein, Max; Wilson, Ryan D.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 4
  • DOI: 10.1021/jp983555d

Molecular structures of supported niobium oxide catalysts under in situ conditions
journal, September 1991

  • Jehng, Jih Mirn; Wachs, Israel E.
  • The Journal of Physical Chemistry, Vol. 95, Issue 19
  • DOI: 10.1021/j100172a049

Co and Ni supported on CeO2 as selective bimetallic catalyst for dry reforming of methane
journal, November 2012

  • Luisetto, Igor; Tuti, Simonetta; Di Bartolomeo, Elisabetta
  • International Journal of Hydrogen Energy, Vol. 37, Issue 21
  • DOI: 10.1016/j.ijhydene.2012.08.006

Dry reforming of methane over CeO2 supported Ni, Co and Ni–Co catalysts
journal, December 2015


Catalytic decomposition of N2O over CeO2 promoted Co3O4 spinel catalyst
journal, September 2007


Highly nanodispersed Gd-doped Ni/ZSM-5 catalyst for enhanced carbon-resistant dry reforming of methane
journal, December 2016


A sintering and carbon-resistant Ni-SBA-15 catalyst prepared by solid-state grinding method for dry reforming of methane
journal, January 2017


CoO x /CeO 2 Nanocomposite Powders:  Synthesis, Characterization, and Reactivity
journal, June 2005

  • Natile, Marta Maria; Glisenti, Antonella
  • Chemistry of Materials, Vol. 17, Issue 13
  • DOI: 10.1021/cm048748u

Molecular/electronic structure–surface acidity relationships of model-supported tungsten oxide catalysts
journal, March 2007


Defect Chemistry of Ceria Nanorods
journal, February 2014

  • Agarwal, S.; Zhu, X.; Hensen, E. J. M.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 8
  • DOI: 10.1021/jp409989y

Controlled Growth and Field-Emission Properties of Cobalt Oxide Nanowalls
journal, July 2005

  • Yu, T.; Zhu, Y. W.; Xu, X. J.
  • Advanced Materials, Vol. 17, Issue 13, p. 1595-1599
  • DOI: 10.1002/adma.200500322

Probing Defect Sites on CeO 2 Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O 2 Adsorption
journal, November 2010

  • Wu, Zili; Li, Meijun; Howe, Jane
  • Langmuir, Vol. 26, Issue 21
  • DOI: 10.1021/la101723w

Structural Characterization of CeO 2 −TiO 2 and V 2 O 5 /CeO 2 −TiO 2 Catalysts by Raman and XPS Techniques
journal, June 2003

  • Reddy, Benjaram M.; Khan, Ataullah; Yamada, Yusuke
  • The Journal of Physical Chemistry B, Vol. 107, Issue 22
  • DOI: 10.1021/jp0344601

The Raman spectra of Co 3 O 4
journal, March 1988

  • Hadjiev, V. G.; Iliev, M. N.; Vergilov, I. V.
  • Journal of Physics C: Solid State Physics, Vol. 21, Issue 7
  • DOI: 10.1088/0022-3719/21/7/007

Direct nitrous oxide decomposition with CoOx-CeO2 catalysts
journal, August 2011


NO reduction with CO on alumina-modified silica-supported palladium and molybdenum-palladium catalysts
journal, May 2008

  • Cónsul, Julia María Díaz; Costilla, Ignacio; Gigola, Carlos Eugenio
  • Applied Catalysis A: General, Vol. 339, Issue 2
  • DOI: 10.1016/j.apcata.2008.01.022

Effect of alkali and alkaline earth metal on Co/CeO 2 catalyst for the water-gas shift reaction of waste derived synthesis gas
journal, February 2018


Hydrodeoxygenation of Phenol over Pd Catalysts. Effect of Support on Reaction Mechanism and Catalyst Deactivation
journal, February 2017

  • de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P.
  • ACS Catalysis, Vol. 7, Issue 3
  • DOI: 10.1021/acscatal.6b02022

The structure of cobalt oxide, Co 3 O 4
journal, February 1973

  • Smith, W. L.; Hobson, A. D.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 29, Issue 2
  • DOI: 10.1107/S0567740873002505

The antiferromagnetic structure deformations in CoO and MnTe
journal, May 1953


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

Dispersion, reduction and catalytic performance of CuO supported on ZrO2-doped TiO2 for NO removal by CO
journal, March 2011


In situ FT-infrared investigation of CO or/and NO interaction with CuO/Ce0.67Zr0.33O2 catalysts
journal, August 2009


Correlation between the physicochemical properties and catalytic performances of CexSn1–xO2 mixed oxides for NO reduction by CO
journal, January 2014


Structure Evolution of Co–CoO x Interface for Higher Alcohol Synthesis from Syngas over Co/CeO 2 Catalysts
journal, August 2018


Works referencing / citing this record:

Catalytic NO reduction by CO over ceria–cobalt oxide catalysts
journal, January 2019

  • Niu, Xiaoran; Lei, Zuotao; Yang, Chunhui
  • New Journal of Chemistry, Vol. 43, Issue 47
  • DOI: 10.1039/c9nj04812j