skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation

Abstract

In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.

Authors:
;  [1];  [2];  [3];  [4];  [4];  [3]
  1. Columbia Univ., New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Univ. of Delaware, Newark, DE (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Columbia Univ., New York, 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:
1246794
Report Number(s):
BNL-111965-2016-JA
Journal ID: ISSN 1433-7851; KC0302010
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 54; Journal Issue: 51; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Marc D. Porosoff, Chen, Jingguang G., Myint, Myat Noe Zin, Kattel, Shyam, Xie, Zhenhua, Gomez, Elaine, and Liu, Ping. Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation. United States: N. p., 2015. Web. doi:10.1002/anie.201508128.
Marc D. Porosoff, Chen, Jingguang G., Myint, Myat Noe Zin, Kattel, Shyam, Xie, Zhenhua, Gomez, Elaine, & Liu, Ping. Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation. United States. doi:10.1002/anie.201508128.
Marc D. Porosoff, Chen, Jingguang G., Myint, Myat Noe Zin, Kattel, Shyam, Xie, Zhenhua, Gomez, Elaine, and Liu, Ping. Tue . "Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation". United States. doi:10.1002/anie.201508128. https://www.osti.gov/servlets/purl/1246794.
@article{osti_1246794,
title = {Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation},
author = {Marc D. Porosoff and Chen, Jingguang G. and Myint, Myat Noe Zin and Kattel, Shyam and Xie, Zhenhua and Gomez, Elaine and Liu, Ping},
abstractNote = {In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.},
doi = {10.1002/anie.201508128},
journal = {Angewandte Chemie (International Edition)},
number = 51,
volume = 54,
place = {United States},
year = {2015},
month = {11}
}

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

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Studies on Dehydrogenation of Ethane in the Presence of CO 2 over Octahedral Molecular Sieve (OMS-2) Catalysts
journal, December 2009


Trends in the catalytic reduction of CO2 by hydrogen over supported monometallic and bimetallic catalysts
journal, May 2013


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

Oxidative Dehydrogenation of Ethane over Cr/ZSM-5 Catalysts Using CO 2 as an Oxidant
journal, November 2006

  • Mimura, Naoki; Okamoto, Masaki; Yamashita, Hiromi
  • The Journal of Physical Chemistry B, Vol. 110, Issue 43
  • DOI: 10.1021/jp061966l

Mitigation of CO2 by Chemical Conversion:  Plausible Chemical Reactions and Promising Products
journal, March 1996

  • Xiaoding, Xu; Moulijn, J. A.
  • Energy & Fuels, Vol. 10, Issue 2, p. 305-325
  • DOI: 10.1021/ef9501511

Identifying trends and descriptors for selective CO 2 conversion to CO over transition metal carbides
journal, January 2015

  • Porosoff, Marc D.; Kattel, Shyam; Li, Wenhui
  • Chemical Communications, Vol. 51, Issue 32
  • DOI: 10.1039/c5cc01545f

Dehydrogenation and oxydehydrogenation of paraffins to olefins
journal, November 2001


Ab initio molecular dynamics for open-shell transition metals
journal, November 1993


Activity and characterization of modified Cr2O3/ZrO2 nano-composite catalysts for oxidative dehydrogenation of ethane to ethylene with CO2
journal, May 2007


The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo 2 C(001) surfaces
journal, January 2014

  • Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 28
  • DOI: 10.1039/c4cp01943a

Non-catalytic pyrolysis of ethane to ethylene in the presence of CO2 with or without limited O2
journal, May 2006

  • Choudhary, Vasant R.; Mondal, Kartick C.; Mulla, Shafeek A. R.
  • Journal of Chemical Sciences, Vol. 118, Issue 3
  • DOI: 10.1007/bf02708286

On the influence of the acid-base character of catalysts on the oxidative dehydrogenation of alkanes
journal, August 1996

  • Concepción, P.; Galli, A.; Nieto, J. M. López
  • Topics in Catalysis, Vol. 3, Issue 3-4
  • DOI: 10.1007/bf02113867

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Effect of Catalyst Structure on Oxidative Dehydrogenation of Ethane and Propane on Alumina-Supported Vanadia
journal, May 2002

  • Argyle, Morris D.; Chen, Kaidong; Bell, Alexis T.
  • Journal of Catalysis, Vol. 208, Issue 1
  • DOI: 10.1006/jcat.2002.3570

Catalytic Technology for Carbon Dioxide Reforming of Methane to Synthesis Gas
journal, October 2009

  • Fan, Mun-Sing; Abdullah, Ahmad Zuhairi; Bhatia, Subhash
  • ChemCatChem, Vol. 1, Issue 2
  • DOI: 10.1002/cctc.200900025

Ceria reoxidation by CO2: A model study
journal, September 2010


Selective Hydrodeoxygenation of Biomass-Derived Oxygenates to Unsaturated Hydrocarbons using Molybdenum Carbide Catalysts
journal, April 2013


Kinetics of the reverse-Boudouard reaction over supported nickel catalysts
journal, August 2006


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Global temperature change
journal, September 2006

  • Hansen, J.; Sato, M.; Ruedy, R.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 39
  • DOI: 10.1073/pnas.0606291103

Projector augmented-wave method
journal, December 1994


A New Type of Strong Metal–Support Interaction and the Production of H 2 through the Transformation of Water on Pt/CeO 2 (111) and Pt/CeO x /TiO 2 (110) Catalysts
journal, May 2012

  • Bruix, Albert; Rodriguez, José A.; Ramírez, Pedro J.
  • Journal of the American Chemical Society, Vol. 134, Issue 21
  • DOI: 10.1021/ja302070k

Oxidative Dehydrogenation of Ethane: Common Principles and Mechanistic Aspects
journal, March 2013

  • Gärtner, Christian A.; van Veen, André C.; Lercher, Johannes A.
  • ChemCatChem, Vol. 5, Issue 11
  • DOI: 10.1002/cctc.201200966

High-performance Cr/H-ZSM-5 catalysts for oxidative dehydrogenation of ethane to ethylene with CO2 as an oxidant
journal, June 2002


Inhomogeneous Electron Gas
journal, March 1973


Selective Conversion of Ethane to Ethene via Oxidative Dehydrogenation Over Ca-doped ThO2 Using CO2 as Oxidant
journal, August 2011


Study on a kinetic model of atmospheric gas oil pyrolysis and coke deposition
journal, May 1993

  • Zou, Renjun; Lou, Qiangkun; Mo, Sihong
  • Industrial & Engineering Chemistry Research, Vol. 32, Issue 5
  • DOI: 10.1021/ie00017a011

Dehydrogenation of ethane over gallium oxide in the presence of carbon dioxide
journal, January 1998

  • Nakagawa, Kiyoharu; Okamura, Masato; Ikenaga, Naoki
  • Chemical Communications, Issue 9
  • DOI: 10.1039/a800184g

Replacing Precious Metals with Carbide Catalysts for Hydrogenation Reactions
journal, March 2015


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/physrevb.13.5188

A first principles study of oxygen reduction reaction on a Pt(111) surface modified by a subsurface transition metal M (M = Ni, Co, or Fe)
journal, January 2011

  • Duan, Zhiyao; Wang, Guofeng
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 45
  • DOI: 10.1039/c1cp21687b

In Situ X-ray Absorption Fine Structure Studies on the Effect of pH on Pt Electronic Density during Aqueous Phase Reforming of Glycerol
journal, September 2012

  • Karim, Ayman M.; Howard, Christopher; Roberts, Benjamin
  • ACS Catalysis, Vol. 2, Issue 11
  • DOI: 10.1021/cs3005049

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


Dehydrogenation of isobutane in the presence of carbon dioxide over supported vanadium oxide catalysts
journal, August 2006

  • Ogonowski, Jan; Skrzyńska, Elżbieta
  • Reaction Kinetics and Catalysis Letters, Vol. 88, Issue 2
  • DOI: 10.1007/s11144-006-0064-9

Dehydrogenation of ethane with carbon dioxide over supported chromium oxide catalysts
journal, March 2000


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


High-performance Cr/H-ZSM-5 catalysts for oxidative dehydrogenation of ethane to ethylene with CO2 as an oxidant
journal, June 2002


Dehydrogenation and oxydehydrogenation of paraffins to olefins
journal, November 2001


Non-catalytic pyrolysis of ethane to ethylene in the presence of CO2 with or without limited O2
journal, May 2006

  • Choudhary, Vasant R.; Mondal, Kartick C.; Mulla, Shafeek A. R.
  • Journal of Chemical Sciences, Vol. 118, Issue 3
  • DOI: 10.1007/BF02708286

Dehydrogenation of ethane with carbon dioxide over supported chromium oxide catalysts
journal, March 2000


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, Vol. 126, Issue 26
  • DOI: 10.1002/ange.201404109

Identifying trends and descriptors for selective CO 2 conversion to CO over transition metal carbides
journal, January 2015

  • Porosoff, Marc D.; Kattel, Shyam; Li, Wenhui
  • Chemical Communications, Vol. 51, Issue 32
  • DOI: 10.1039/C5CC01545F

The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo 2 C(001) surfaces
journal, January 2014

  • Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 28
  • DOI: 10.1039/C4CP01943A

Inhomogeneous Electron Gas
journal, November 1964


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Ab initio molecular dynamics for open-shell transition metals
journal, November 1993


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Projector augmented-wave method
journal, December 1994


Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


    Works referencing / citing this record:

    Activation Pathway of C‐H and C–C Bonds of Ethane by Pd Atom with CO 2 as a Soft Oxidant
    journal, August 2019


    Carbon dioxide reduction in tandem with light-alkane dehydrogenation
    journal, September 2019


    Mechanistic study of dry reforming of ethane by CO 2 on a bimetallic PtNi(111) model surface
    journal, January 2018

    • Kattel, Shyam; Chen, Jingguang G.; Liu, Ping
    • Catalysis Science & Technology, Vol. 8, Issue 15
    • DOI: 10.1039/c8cy00880a

    Carbon Dioxide Promotes Dehydrogenation in the Equimolar C 2 H 2 -CO 2 Reaction to Synthesize Carbon Nanotubes
    journal, January 2018


    The effects of bimetallic interactions for CO 2 ‐assisted oxidative dehydrogenation and dry reforming of propane
    journal, June 2019

    • Gomez, Elaine; Xie, Zhenhua; Chen, Jingguang G.
    • AIChE Journal, Vol. 65, Issue 8
    • DOI: 10.1002/aic.16670

    Effect of Oxide Support on Catalytic Performance of FeNi‐based Catalysts for CO 2 ‐assisted Oxidative Dehydrogenation of Ethane
    journal, November 2019


    Active sites for tandem reactions of CO 2 reduction and ethane dehydrogenation
    journal, July 2018

    • Yan, Binhang; Yao, Siyu; Kattel, Shyam
    • Proceedings of the National Academy of Sciences, Vol. 115, Issue 33
    • DOI: 10.1073/pnas.1806950115