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

Title: Combining CO2 Reduction with Ethane Oxidative Dehydrogenation by Oxygen-Modification of Molybdenum Carbide

Abstract

The surface properties that determine the selectivity of Mo2C catalysts in ethane oxidative dehydrogenation with CO2 as a soft oxidant were investigated using a combination of pulse experiments and in-situ spectroscopic methods. Oxygen modification was discovered to be crucial for inhibiting the cleavage of the C–C bond in ethane and enhancing the production of ethylene. Here, the addition of the Fe promoter accelerated the formation of surface oxygen species and stabilized them from reduction by ethane, leading to a shorter induction period, higher ethylene yield, and improved stability.

Authors:
 [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [4]; ORCiD logo [5]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Columbia Univ., New York, NY (United States); Xi'an Jiaotong Univ., Xi'an (China)
  3. Stony Brook Univ., Stony Brook, NY (United States)
  4. Columbia Univ., New York, NY (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); 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:
1462423
Report Number(s):
BNL-207911-2018-JAAM
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; carbon dioxide; ethane; oxidative dehydrogenation; oxygen-modified molybdenum carbide; pulse reactor experiment

Citation Formats

Yao, Siyu, Yan, Binhang, Jiang, Zhao, Liu, Zongyuan, Wu, Qiyuan, Lee, Ji Hoon, and Chen, Jingguang G. Combining CO2 Reduction with Ethane Oxidative Dehydrogenation by Oxygen-Modification of Molybdenum Carbide. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b00541.
Yao, Siyu, Yan, Binhang, Jiang, Zhao, Liu, Zongyuan, Wu, Qiyuan, Lee, Ji Hoon, & Chen, Jingguang G. Combining CO2 Reduction with Ethane Oxidative Dehydrogenation by Oxygen-Modification of Molybdenum Carbide. United States. https://doi.org/10.1021/acscatal.8b00541
Yao, Siyu, Yan, Binhang, Jiang, Zhao, Liu, Zongyuan, Wu, Qiyuan, Lee, Ji Hoon, and Chen, Jingguang G. Wed . "Combining CO2 Reduction with Ethane Oxidative Dehydrogenation by Oxygen-Modification of Molybdenum Carbide". United States. https://doi.org/10.1021/acscatal.8b00541. https://www.osti.gov/servlets/purl/1462423.
@article{osti_1462423,
title = {Combining CO2 Reduction with Ethane Oxidative Dehydrogenation by Oxygen-Modification of Molybdenum Carbide},
author = {Yao, Siyu and Yan, Binhang and Jiang, Zhao and Liu, Zongyuan and Wu, Qiyuan and Lee, Ji Hoon and Chen, Jingguang G.},
abstractNote = {The surface properties that determine the selectivity of Mo2C catalysts in ethane oxidative dehydrogenation with CO2 as a soft oxidant were investigated using a combination of pulse experiments and in-situ spectroscopic methods. Oxygen modification was discovered to be crucial for inhibiting the cleavage of the C–C bond in ethane and enhancing the production of ethylene. Here, the addition of the Fe promoter accelerated the formation of surface oxygen species and stabilized them from reduction by ethane, leading to a shorter induction period, higher ethylene yield, and improved stability.},
doi = {10.1021/acscatal.8b00541},
journal = {ACS Catalysis},
number = 6,
volume = 8,
place = {United States},
year = {2018},
month = {5}
}

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

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Catalytic performance of C2H6 ODH reaction on Mo2C with different pretreatments. (A) ethane conversion; (B) ethylene selectivity and (C) ethylene yield.

Save / Share:

Works referenced in this record:

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


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

Late-Metal Catalysts for Ethylene Homo- and Copolymerization
journal, April 2000

  • Ittel, Steven D.; Johnson, Lynda K.; Brookhart, Maurice
  • Chemical Reviews, Vol. 100, Issue 4
  • DOI: 10.1021/cr9804644

Recent advancements in ethylene and propylene production using the UOP/Hydro MTO process
journal, October 2005


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


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

Role of Carbon Dioxide in the Dehydrogenation of Ethane over Gallium-Loaded Catalysts
journal, October 2001

  • Nakagawa, Kiyoharu; Kajita, Chiaki; Okumura, Kimito
  • Journal of Catalysis, Vol. 203, Issue 1
  • DOI: 10.1006/jcat.2001.3306

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

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


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


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


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

Effects of oxygen coverage on rates and selectivity of propane-CO2 reactions on molybdenum carbide
journal, January 2018


Molybdenum carbide catalysts I. Synthesis of unsupported powders
journal, July 1987


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Ab initiomolecular dynamics for liquid metals
journal, January 1993


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


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


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Stability of β-Mo 2 C Facets from ab Initio Atomistic Thermodynamics
journal, October 2011

  • Wang, Tao; Liu, Xingwu; Wang, Shengguang
  • The Journal of Physical Chemistry C, Vol. 115, Issue 45
  • DOI: 10.1021/jp205950x

Molybdenum carbide catalysed hydrogen production from formic acid – A density functional theory study
journal, January 2014


195. Dimolybdenum carbide
journal, December 1960

  • Fries, R. J.; Kempter, Charles P.
  • Analytical Chemistry, Vol. 32, Issue 13
  • DOI: 10.1021/ac50153a061

Surface Chemistry of Transition Metal Carbides
journal, January 2005

  • Hwu, Henry H.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 105, Issue 1
  • DOI: 10.1021/cr0204606

Conversion of methane to benzene over Mo2C and Mo2C/ZSM-5 catalysts
journal, January 1996

  • Solymosi, F.; Sz�ke, A.; Cser�nyi, J.
  • Catalysis Letters, Vol. 39, Issue 3-4
  • DOI: 10.1007/BF00805576

Oxidation stability of Mo2C catalysts under fuel reforming conditions
journal, October 2003


Adsorption and Reaction of CO 2 on Mo 2 C Catalyst
journal, September 2002

  • Solymosi, F.; Oszkó, A.; Bánsági, T.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 37
  • DOI: 10.1021/jp0203696

Chemical Titration and Transient Kinetic Studies of Site Requirements in Mo 2 C-Catalyzed Vapor Phase Anisole Hydrodeoxygenation
journal, June 2015


Characterization of Molybdenum Carbides for Methane Reforming by TPR, XRD, and XPS
journal, September 2001

  • Oshikawa, Katsuhiko; Nagai, Masatoshi; Omi, Shinzo
  • The Journal of Physical Chemistry B, Vol. 105, Issue 38
  • DOI: 10.1021/jp0111867

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


C–H bond activation of methane on clean and oxygen pre-covered metals: A systematic theoretical study
journal, August 2011


Works referencing / citing this record:

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

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


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.