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

This content will become publicly available on September 10, 2020

Title: Carbon dioxide reduction in tandem with light-alkane dehydrogenation

Abstract

A greenhouse gas and mild oxidant, CO 2 can effect the oxidative dehydrogenation (CO 2-ODH) of light alkanes over heterogeneous catalysts. These catalysts are bifunctional in that they mediate CO 2 reduction while oxidizing the alkanes, most notably the C 2–C 4 components in shale gas. In this way, one obtains CO and alkenes as value-added products. Although desirable, this transformation has proven challenging in terms of catalyst design, with most catalysts for the CO 2-ODH being metal oxides that typically undergo rapid deactivation. More recently, bimetallic catalysts have been identified as promising systems to activate alkanes by either selectively cleaving C–H bonds to produce alkenes or breaking all the C–C and C–H bonds to produce the dry reforming products CO and H 2. This Review describes general trends in the CO 2-ODH of light alkanes. Furthermore, we will outline how to use a combined approach involving flow reactor experiments, in operando characterization and density functional theory to determine whether a catalyst is intrinsically active for CO 2-ODH or dry reforming.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Columbia Univ., New York, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Tsinghua Univ., Beijing (China)
  3. Columbia Univ., New York, NY (United States); Florida A & M University, Tallahassee, FL (United States)
  4. Columbia Univ., New York, 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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1580234
Report Number(s):
BNL-212449-2019-JAAM
Journal ID: ISSN 2397-3358
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Reviews Chemistry
Additional Journal Information:
Journal Volume: 3; Journal Issue: 11; Journal ID: ISSN 2397-3358
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Gomez, Elaine, Yan, Binhang, Kattel, Shyam, and Chen, Jingguang G. Carbon dioxide reduction in tandem with light-alkane dehydrogenation. United States: N. p., 2019. Web. doi:10.1038/s41570-019-0128-9.
Gomez, Elaine, Yan, Binhang, Kattel, Shyam, & Chen, Jingguang G. Carbon dioxide reduction in tandem with light-alkane dehydrogenation. United States. doi:10.1038/s41570-019-0128-9.
Gomez, Elaine, Yan, Binhang, Kattel, Shyam, and Chen, Jingguang G. Tue . "Carbon dioxide reduction in tandem with light-alkane dehydrogenation". United States. doi:10.1038/s41570-019-0128-9.
@article{osti_1580234,
title = {Carbon dioxide reduction in tandem with light-alkane dehydrogenation},
author = {Gomez, Elaine and Yan, Binhang and Kattel, Shyam and Chen, Jingguang G.},
abstractNote = {A greenhouse gas and mild oxidant, CO2 can effect the oxidative dehydrogenation (CO2-ODH) of light alkanes over heterogeneous catalysts. These catalysts are bifunctional in that they mediate CO2 reduction while oxidizing the alkanes, most notably the C2–C4 components in shale gas. In this way, one obtains CO and alkenes as value-added products. Although desirable, this transformation has proven challenging in terms of catalyst design, with most catalysts for the CO2-ODH being metal oxides that typically undergo rapid deactivation. More recently, bimetallic catalysts have been identified as promising systems to activate alkanes by either selectively cleaving C–H bonds to produce alkenes or breaking all the C–C and C–H bonds to produce the dry reforming products CO and H2. This Review describes general trends in the CO2-ODH of light alkanes. Furthermore, we will outline how to use a combined approach involving flow reactor experiments, in operando characterization and density functional theory to determine whether a catalyst is intrinsically active for CO2-ODH or dry reforming.},
doi = {10.1038/s41570-019-0128-9},
journal = {Nature Reviews Chemistry},
number = 11,
volume = 3,
place = {United States},
year = {2019},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on September 10, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Methane activation: the past and future
journal, January 2014

  • Tang, Pei; Zhu, Qingjun; Wu, Zhaoxuan
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE00604F

Methanol to Olefins (MTO): From Fundamentals to Commercialization
journal, February 2015


Hierarchical SAPO-34/18 zeolite with low acid site density for converting methanol to olefins
journal, September 2014


New Trends in Olefin Production
journal, April 2017


Highly Tunable Selectivity for Syngas-Derived Alkenes over Zinc and Sodium-Modulated Fe 5 C 2 Catalyst
journal, July 2016

  • Zhai, Peng; Xu, Cong; Gao, Rui
  • Angewandte Chemie International Edition, Vol. 55, Issue 34
  • DOI: 10.1002/anie.201603556

CO2 as a soft oxidant for oxidative dehydrogenation reaction: An eco benign process for industry
journal, December 2016


CO 2 Activation over Catalytic Surfaces
journal, October 2017

  • Álvarez, Andrea; Borges, Marta; Corral-Pérez, Juan José
  • ChemPhysChem, Vol. 18, Issue 22
  • DOI: 10.1002/cphc.201700782

Support effect in dehydrogenation of propane in the presence of CO2 over supported gallium oxide catalysts
journal, April 2006


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


Catalytic Conversion of Alkanes to Olefins by Carbon Dioxide Oxidative DehydrogenationA Review
journal, July 2004


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

Carbon dioxide utilization as a soft oxidant and promoter in catalysis
journal, January 2012

  • Ansari, Mohd Bismillah; Park, Sang-Eon
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee22409g

Oxidative dehydrogenation of propane to propylene with carbon dioxide
journal, January 2018


Thermodynamic Equilibrium Analysis of Propane Dehydrogenation with Carbon Dioxide and Side Reactions
journal, March 2015

  • Zangeneh, Farnaz Tahriri; Taeb, Abbas; Gholivand, Khodayar
  • Chemical Engineering Communications, Vol. 203, Issue 4
  • DOI: 10.1080/00986445.2015.1017638

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


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

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


Dehydrogenation of ethane to ethylene over a highly efficient Ga2O3/HZSM-5 catalyst in the presence of CO2
journal, March 2009


Oxidative Dehydrogenation of Ethane with CO 2 over Flame-Made Ga-Loaded TiO 2
journal, December 2014

  • Koirala, Rajesh; Buechel, Robert; Krumeich, Frank
  • ACS Catalysis, Vol. 5, Issue 2
  • DOI: 10.1021/cs500685d

Oxidative dehydrogenation of ethane over Co–BaCO3 catalysts using CO2 as oxidant: effects of Co promoter
journal, May 2007


Silica is preferred over various single and mixed oxides as support for CO 2 -assisted cobalt-catalyzed oxidative dehydrogenation of ethane
journal, October 2016


Na2WO4/Mn/SiO2 catalyst for oxidative dehydrogenation of ethane using CO2 as oxidant
journal, November 2009


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


Selective oxidehydrogenation of ethane with CO2 over CeO2-based catalysts
journal, August 2000


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


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

Chromium oxide supported on ZSM-5 as a novel efficient catalyst for dehydrogenation of propane with CO2
journal, November 2011


Oxidative Dehydrogenation of Ethane to Ethylene with CO 2 over Fe−Cr/ZrO 2 Catalysts
journal, August 2009

  • Deng, Shuang; Li, Songgeng; Li, Huiquan
  • Industrial & Engineering Chemistry Research, Vol. 48, Issue 16
  • DOI: 10.1021/ie9007387

Oxidative dehydrogenation of ethane and propane: How far from commercial implementation?
journal, September 2007


The Relationship between the Electronic and Redox Properties of Dispersed Metal Oxides and Their Turnover Rates in Oxidative Dehydrogenation Reactions
journal, July 2002

  • Chen, Kaidong; Bell, Alexis T.; Iglesia, Enrique
  • Journal of Catalysis, Vol. 209, Issue 1
  • DOI: 10.1006/jcat.2002.3620

Size-Dependent Catalytic Activity of Supported Vanadium Oxide Species: Oxidative Dehydrogenation of Propane
journal, May 2014

  • Rozanska, Xavier; Fortrie, Remy; Sauer, Joachim
  • Journal of the American Chemical Society, Vol. 136, Issue 21
  • DOI: 10.1021/ja503130z

DFT Study of CO 2 Adsorption and Hydrogenation on the In 2 O 3 Surface
journal, March 2012

  • Ye, Jingyun; Liu, Changjun; Ge, Qingfeng
  • The Journal of Physical Chemistry C, Vol. 116, Issue 14
  • DOI: 10.1021/jp3004773

Periodic Density Functional Theory Study of Propane Dehydrogenation over Perfect Ga 2 O 3 (100) Surface
journal, December 2008

  • Liu, Yan; Li, Zhen Hua; Lu, Jing
  • The Journal of Physical Chemistry C, Vol. 112, Issue 51
  • DOI: 10.1021/jp807864z

Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts
journal, August 2012

  • Yu, Weiting; Porosoff, Marc D.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 112, Issue 11, p. 5780-5817
  • DOI: 10.1021/cr300096b

Challenges and opportunities in correlating bimetallic model surfaces and supported catalysts
journal, December 2013


Catalytic reduction of CO 2 by H 2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities
journal, January 2016

  • Porosoff, Marc D.; Yan, Binhang; Chen, Jingguang G.
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE02657A

Catalytic Properties of Ceria and CeO 2 -Containing Materials
journal, November 1996


Carbon dioxide activation and dissociation on ceria (110): A density functional theory study
journal, January 2013

  • Cheng, Zhuo; Sherman, Brent J.; Lo, Cynthia S.
  • The Journal of Chemical Physics, Vol. 138, Issue 1, Article No. 014702
  • DOI: 10.1063/1.4773248

A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO 2 mitigation
journal, July 2010

  • Chueh, William C.; Haile, Sossina M.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923
  • DOI: 10.1098/rsta.2010.0114

Oxygen exchange mechanism between isotopic CO2 and Pt/CeO2
journal, June 2008


Reforming and oxidative dehydrogenation of ethane with CO2 as a soft oxidant over bimetallic catalysts
journal, November 2016


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

Catalytic properties of early transition metal nitrides and carbides: n-butane hydrogenolysis, dehydrogenation and isomerization
journal, July 1999


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

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


Identifying Different Types of Catalysts for CO 2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation
journal, November 2015

  • Porosoff, Marc D.; Myint, Myat Noe Zin; Kattel, Shyam
  • Angewandte Chemie International Edition, Vol. 54, Issue 51
  • DOI: 10.1002/anie.201508128

Combining CO 2 Reduction with Ethane Oxidative Dehydrogenation by Oxygen-Modification of Molybdenum Carbide
journal, May 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