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Title: Influence of copper on nickel-based catalysts in the conversion of glycerol

Abstract

The catalytic transformation of glycerol to value-added compounds was investigated over bimetallic Ni-Cu/γ-Al2O3 catalysts with Ni/Cu atomic ratios of 8/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8. XPS analysis revealed that the surface composition of the catalyst exhibited progressive enrichment of Cu as its content in the catalyst increased. H2-chemisorption indicated that the total number of exposed Ni atoms decreased as the Cu content increased. As a result, deep hydrogenolysis to produce CH4 was inhibited by the addition of Cu to the Ni catalyst, yielding higher selectivity towards the dehydration products of glycerol such as hydroxyacetone. FTIR spectra of adsorbed CO reveals that Cu asserts both geometric and electronic effects on the adsorption properties of Ni. The geometrical effect is visualized by the progressive disappearance of the bridge-bound adsorbed CO on metallic Ni by the incorporation of Cu. This suggests that the deep hydrogenolysis of glycerol to CH4 formation requires an ensemble of adjacent active Ni atoms. The electronic effect of Cu on Ni is indicated by the red shift of the IR peak of adsorbed CO as the Cu content increases. The electronic interaction between Cu and Ni species was also substantiated by XANES results. HTREM revealed metal particlesmore » very well distributed on the support with particle size of 1.5 to 5 nm. The Ni-Cu samples were not a total intermetallic alloys. We also gratefully acknowledge the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division for the support of this work. The research related to the FTIR of adsorption of CO (Proposal 48209) was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1178493
Report Number(s):
PNNL-SA-106690
48593; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Applied Catalysis. B, Environmental, 166-167:166-180
Additional Journal Information:
Journal Name: Applied Catalysis. B, Environmental, 166-167:166-180
Country of Publication:
United States
Language:
English
Subject:
hydrogenolysis; dehydration; glycerol; nickel; copper; catalyst, reduction; Environmental Molecular Sciences Laboratory

Citation Formats

Miranda, Barbara C., Chimentao, Ricardo J., Szanyi, Janos, Braga, Adriano H., Santos, Joao Batista O., Gispert-Guirado, Francesc, Llorca, Jordi, and Medina, Francesc. Influence of copper on nickel-based catalysts in the conversion of glycerol. United States: N. p., 2015. Web. doi:10.1016/j.apcatb.2014.11.019.
Miranda, Barbara C., Chimentao, Ricardo J., Szanyi, Janos, Braga, Adriano H., Santos, Joao Batista O., Gispert-Guirado, Francesc, Llorca, Jordi, & Medina, Francesc. Influence of copper on nickel-based catalysts in the conversion of glycerol. United States. doi:10.1016/j.apcatb.2014.11.019.
Miranda, Barbara C., Chimentao, Ricardo J., Szanyi, Janos, Braga, Adriano H., Santos, Joao Batista O., Gispert-Guirado, Francesc, Llorca, Jordi, and Medina, Francesc. Fri . "Influence of copper on nickel-based catalysts in the conversion of glycerol". United States. doi:10.1016/j.apcatb.2014.11.019.
@article{osti_1178493,
title = {Influence of copper on nickel-based catalysts in the conversion of glycerol},
author = {Miranda, Barbara C. and Chimentao, Ricardo J. and Szanyi, Janos and Braga, Adriano H. and Santos, Joao Batista O. and Gispert-Guirado, Francesc and Llorca, Jordi and Medina, Francesc},
abstractNote = {The catalytic transformation of glycerol to value-added compounds was investigated over bimetallic Ni-Cu/γ-Al2O3 catalysts with Ni/Cu atomic ratios of 8/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8. XPS analysis revealed that the surface composition of the catalyst exhibited progressive enrichment of Cu as its content in the catalyst increased. H2-chemisorption indicated that the total number of exposed Ni atoms decreased as the Cu content increased. As a result, deep hydrogenolysis to produce CH4 was inhibited by the addition of Cu to the Ni catalyst, yielding higher selectivity towards the dehydration products of glycerol such as hydroxyacetone. FTIR spectra of adsorbed CO reveals that Cu asserts both geometric and electronic effects on the adsorption properties of Ni. The geometrical effect is visualized by the progressive disappearance of the bridge-bound adsorbed CO on metallic Ni by the incorporation of Cu. This suggests that the deep hydrogenolysis of glycerol to CH4 formation requires an ensemble of adjacent active Ni atoms. The electronic effect of Cu on Ni is indicated by the red shift of the IR peak of adsorbed CO as the Cu content increases. The electronic interaction between Cu and Ni species was also substantiated by XANES results. HTREM revealed metal particles very well distributed on the support with particle size of 1.5 to 5 nm. The Ni-Cu samples were not a total intermetallic alloys. We also gratefully acknowledge the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division for the support of this work. The research related to the FTIR of adsorption of CO (Proposal 48209) was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.},
doi = {10.1016/j.apcatb.2014.11.019},
journal = {Applied Catalysis. B, Environmental, 166-167:166-180},
number = ,
volume = ,
place = {United States},
year = {2015},
month = {5}
}