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Title: Sulfur-resistant and regenerable Ni/Co spinel-based catalysts for methane dry reforming

Abstract

Oxide-supported metal catalysts were prepared in this study by thermal impregnation of highly crystalline and highly-faceted starting spinels of the form (M 0.75Mg 0.25)Al 2O 4, where M = Ni, Co, or Cu and mixtures thereof. In situ reduction at 900°C extracts the transition metals from the oxide, and the resulting catalysts contain metal crystallites with particle sizes of ~100 nm and exceedingly low dispersion, but show high activity for dry reforming of methane with turnover frequencies as large as 3.9 at 850°C. The Ni 0.375Cu 0.375Mg 0.25Al 2O 4 catalyst shows stable methane conversion out to 12 hours on stream without performance-degrading coking. For the Ni/Co catalysts, the reforming activity and sulfur tolerance are both functions of the Ni/Co ratio and the synthesis temperature of the starting spinel, with Ni 0.375Co 0.375Mg 0.25Al 2O 4 synthesized at 1500°C displaying fast reaction kinetics even in the presence of 20 ppm H 2S. High reforming activity is attributed to long linear lengths of high-perfection facet edges and corners on the metal crystallites. Sulfur tolerance seems to be improved by a combination of the oxygen storage capacity of the defective spinel support and its faceting that provides additional reaction sites for activationmore » of CO 2.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [3];  [3];  [3]
  1. Alfred Univ., NY (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1311251
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 5; Journal Issue: 9; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Misture, S. T., McDevitt, K. M., Glass, K. C., Edwards, D. D., Howe, Jane Y., Rector, K. D., He, H., and Vogel, S. C. Sulfur-resistant and regenerable Ni/Co spinel-based catalysts for methane dry reforming. United States: N. p., 2015. Web. doi:10.1039/C5CY00800J.
Misture, S. T., McDevitt, K. M., Glass, K. C., Edwards, D. D., Howe, Jane Y., Rector, K. D., He, H., & Vogel, S. C. Sulfur-resistant and regenerable Ni/Co spinel-based catalysts for methane dry reforming. United States. doi:10.1039/C5CY00800J.
Misture, S. T., McDevitt, K. M., Glass, K. C., Edwards, D. D., Howe, Jane Y., Rector, K. D., He, H., and Vogel, S. C. Thu . "Sulfur-resistant and regenerable Ni/Co spinel-based catalysts for methane dry reforming". United States. doi:10.1039/C5CY00800J.
@article{osti_1311251,
title = {Sulfur-resistant and regenerable Ni/Co spinel-based catalysts for methane dry reforming},
author = {Misture, S. T. and McDevitt, K. M. and Glass, K. C. and Edwards, D. D. and Howe, Jane Y. and Rector, K. D. and He, H. and Vogel, S. C.},
abstractNote = {Oxide-supported metal catalysts were prepared in this study by thermal impregnation of highly crystalline and highly-faceted starting spinels of the form (M0.75Mg0.25)Al2O4, where M = Ni, Co, or Cu and mixtures thereof. In situ reduction at 900°C extracts the transition metals from the oxide, and the resulting catalysts contain metal crystallites with particle sizes of ~100 nm and exceedingly low dispersion, but show high activity for dry reforming of methane with turnover frequencies as large as 3.9 at 850°C. The Ni0.375Cu0.375Mg0.25Al2O4 catalyst shows stable methane conversion out to 12 hours on stream without performance-degrading coking. For the Ni/Co catalysts, the reforming activity and sulfur tolerance are both functions of the Ni/Co ratio and the synthesis temperature of the starting spinel, with Ni0.375Co0.375Mg0.25Al2O4 synthesized at 1500°C displaying fast reaction kinetics even in the presence of 20 ppm H2S. High reforming activity is attributed to long linear lengths of high-perfection facet edges and corners on the metal crystallites. Sulfur tolerance seems to be improved by a combination of the oxygen storage capacity of the defective spinel support and its faceting that provides additional reaction sites for activation of CO2.},
doi = {10.1039/C5CY00800J},
journal = {Catalysis Science and Technology},
issn = {2044-4753},
number = 9,
volume = 5,
place = {United States},
year = {2015},
month = {7}
}

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