Effect of pretreatment conditions on acidity and dehydration activity of CeO2-MeOx catalysts

Muthu Kumaran Gnanamani; Richard Garcia; Gary Jacobs; Kinga Góra-Marek; Donald C. Cronauer; A. Jeremy Kropf; Christopher L. Marshall

doi:10.1016/j.apcata.2020.117722

Effect of pretreatment conditions on acidity and dehydration activity of CeO₂-MeO_x catalysts

Muthu Kumaran Gnanamani, Richard Garcia, Gary Jacobs, Kinga Góra-Marek, Donald C. Cronauer, A. Jeremy Kropf, Christopher L. Marshall

Center for Applied Energy Research (CAER)

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

A series of MeO_x-modified CeO₂ (CeO₂-MnO_x, CeO₂-ZnO, CeO₂-MgO, CeO₂-CaO, and CeO₂-Na₂O) catalysts were prepared by the impregnation of CeO₂ with corresponding metal nitrates. Acidity and oxidation state of cerium were investigated on both oxidized and reduced catalysts by employing Fourier Transform Infrared spectroscopy (FTIR) on adsorbed pyridine and in situ H₂-Temperature Programmed Reduction/X-ray Absorption Spectroscopy (H₂-TPR/XAS) techniques, respectively. Metal oxide addition tended to alter both type and number of acid sites on ceria. EXAFS data showed a significant difference in N_Ce-O between unmodified and CeO₂-MeO_x, suggesting that added MeO_x interferes with vacancy formation on ceria during reduction. In comparison with air-pretreated samples, H₂-pretreated ones under similar conversion of 1,5 pentanediol exhibited a higher selectivity towards linear alcohols. Alcohol conversion found to correlate with total acidity (i.e., Brønsted and Lewis). CeO₂ benefited from the addition of alkali (Na) or alkaline earth metals (Mg, Ca) by producing unsaturated alcohols.

Original language	English
Article number	117722
Journal	Applied Catalysis A: General
Volume	602
DOIs	https://doi.org/10.1016/j.apcata.2020.117722
State	Published - Jul 25 2020

Bibliographical note

Funding Information:
The work carried out at the CAER was supported in part by funding from the Commonwealth of Kentucky . Research conducted at UTSA was supported by UTSA, the State of Texas, and the STARs program . Richard Garcia would like to acknowledge funding from a UTSA College of Engineering Scholarship . His work was also supported by the USDA National Institute of Food and Agriculture, Interdisciplinary Hands-on Research Traineeship and Extension Experiential Learning in Bioenergy/Natural Resources/Economics/Rural project, U-GREAT (Undergraduate Research, Education and Training) program ( 2016-67032-24984 ). Argonne’s research was supported in part by the U.S. Department of Energy (DOE) , Office of Fossil Energy, National Energy Technology Laboratory (NETL) . Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions .

Funding Information:
The work carried out at the CAER was supported in part by funding from the Commonwealth of Kentucky. Research conducted at UTSA was supported by UTSA, the State of Texas, and the STARs program. Richard Garcia would like to acknowledge funding from a UTSA College of Engineering Scholarship. His work was also supported by the USDA National Institute of Food and Agriculture, Interdisciplinary Hands-on Research Traineeship and Extension Experiential Learning in Bioenergy/Natural Resources/Economics/Rural project, U-GREAT (Undergraduate Research, Education and Training) program (2016-67032-24984). Argonne's research was supported in part by the U.S. Department of Energy (DOE), Office of Fossil Energy, National Energy Technology Laboratory (NETL). Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions.

Publisher Copyright:
© 2020 Elsevier B.V.

Keywords

1,5-Pentanediol
Acidity
CeO-MeO
Dehydration
X-ray absorption spectroscopy

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology

Access to Document

10.1016/j.apcata.2020.117722

Cite this

@article{bd97bac9f17a4b74a9ce2338aed38614,

title = "Effect of pretreatment conditions on acidity and dehydration activity of CeO2-MeOx catalysts",

abstract = "A series of MeOx-modified CeO2 (CeO2-MnOx, CeO2-ZnO, CeO2-MgO, CeO2-CaO, and CeO2-Na2O) catalysts were prepared by the impregnation of CeO2 with corresponding metal nitrates. Acidity and oxidation state of cerium were investigated on both oxidized and reduced catalysts by employing Fourier Transform Infrared spectroscopy (FTIR) on adsorbed pyridine and in situ H2-Temperature Programmed Reduction/X-ray Absorption Spectroscopy (H2-TPR/XAS) techniques, respectively. Metal oxide addition tended to alter both type and number of acid sites on ceria. EXAFS data showed a significant difference in NCe-O between unmodified and CeO2-MeOx, suggesting that added MeOx interferes with vacancy formation on ceria during reduction. In comparison with air-pretreated samples, H2-pretreated ones under similar conversion of 1,5 pentanediol exhibited a higher selectivity towards linear alcohols. Alcohol conversion found to correlate with total acidity (i.e., Br{\o}nsted and Lewis). CeO2 benefited from the addition of alkali (Na) or alkaline earth metals (Mg, Ca) by producing unsaturated alcohols.",

keywords = "1,5-Pentanediol, Acidity, CeO-MeO, Dehydration, X-ray absorption spectroscopy",

author = "Gnanamani, {Muthu Kumaran} and Richard Garcia and Gary Jacobs and Kinga G{\'o}ra-Marek and Cronauer, {Donald C.} and Kropf, {A. Jeremy} and Marshall, {Christopher L.}",

note = "Funding Information: The work carried out at the CAER was supported in part by funding from the Commonwealth of Kentucky . Research conducted at UTSA was supported by UTSA, the State of Texas, and the STARs program . Richard Garcia would like to acknowledge funding from a UTSA College of Engineering Scholarship . His work was also supported by the USDA National Institute of Food and Agriculture, Interdisciplinary Hands-on Research Traineeship and Extension Experiential Learning in Bioenergy/Natural Resources/Economics/Rural project, U-GREAT (Undergraduate Research, Education and Training) program ( 2016-67032-24984 ). Argonne{\textquoteright}s research was supported in part by the U.S. Department of Energy (DOE) , Office of Fossil Energy, National Energy Technology Laboratory (NETL) . Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions . Funding Information: The work carried out at the CAER was supported in part by funding from the Commonwealth of Kentucky. Research conducted at UTSA was supported by UTSA, the State of Texas, and the STARs program. Richard Garcia would like to acknowledge funding from a UTSA College of Engineering Scholarship. His work was also supported by the USDA National Institute of Food and Agriculture, Interdisciplinary Hands-on Research Traineeship and Extension Experiential Learning in Bioenergy/Natural Resources/Economics/Rural project, U-GREAT (Undergraduate Research, Education and Training) program (2016-67032-24984). Argonne's research was supported in part by the U.S. Department of Energy (DOE), Office of Fossil Energy, National Energy Technology Laboratory (NETL). Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. Publisher Copyright: {\textcopyright} 2020 Elsevier B.V.",

year = "2020",

month = jul,

day = "25",

doi = "10.1016/j.apcata.2020.117722",

language = "English",

volume = "602",

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T1 - Effect of pretreatment conditions on acidity and dehydration activity of CeO2-MeOx catalysts

AU - Gnanamani, Muthu Kumaran

AU - Garcia, Richard

AU - Jacobs, Gary

AU - Góra-Marek, Kinga

AU - Cronauer, Donald C.

AU - Kropf, A. Jeremy

AU - Marshall, Christopher L.

N1 - Funding Information: The work carried out at the CAER was supported in part by funding from the Commonwealth of Kentucky . Research conducted at UTSA was supported by UTSA, the State of Texas, and the STARs program . Richard Garcia would like to acknowledge funding from a UTSA College of Engineering Scholarship . His work was also supported by the USDA National Institute of Food and Agriculture, Interdisciplinary Hands-on Research Traineeship and Extension Experiential Learning in Bioenergy/Natural Resources/Economics/Rural project, U-GREAT (Undergraduate Research, Education and Training) program ( 2016-67032-24984 ). Argonne’s research was supported in part by the U.S. Department of Energy (DOE) , Office of Fossil Energy, National Energy Technology Laboratory (NETL) . Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions . Funding Information: The work carried out at the CAER was supported in part by funding from the Commonwealth of Kentucky. Research conducted at UTSA was supported by UTSA, the State of Texas, and the STARs program. Richard Garcia would like to acknowledge funding from a UTSA College of Engineering Scholarship. His work was also supported by the USDA National Institute of Food and Agriculture, Interdisciplinary Hands-on Research Traineeship and Extension Experiential Learning in Bioenergy/Natural Resources/Economics/Rural project, U-GREAT (Undergraduate Research, Education and Training) program (2016-67032-24984). Argonne's research was supported in part by the U.S. Department of Energy (DOE), Office of Fossil Energy, National Energy Technology Laboratory (NETL). Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. MRCAT operations are supported by the Department of Energy and the MRCAT member institutions. Publisher Copyright: © 2020 Elsevier B.V.

PY - 2020/7/25

Y1 - 2020/7/25

N2 - A series of MeOx-modified CeO2 (CeO2-MnOx, CeO2-ZnO, CeO2-MgO, CeO2-CaO, and CeO2-Na2O) catalysts were prepared by the impregnation of CeO2 with corresponding metal nitrates. Acidity and oxidation state of cerium were investigated on both oxidized and reduced catalysts by employing Fourier Transform Infrared spectroscopy (FTIR) on adsorbed pyridine and in situ H2-Temperature Programmed Reduction/X-ray Absorption Spectroscopy (H2-TPR/XAS) techniques, respectively. Metal oxide addition tended to alter both type and number of acid sites on ceria. EXAFS data showed a significant difference in NCe-O between unmodified and CeO2-MeOx, suggesting that added MeOx interferes with vacancy formation on ceria during reduction. In comparison with air-pretreated samples, H2-pretreated ones under similar conversion of 1,5 pentanediol exhibited a higher selectivity towards linear alcohols. Alcohol conversion found to correlate with total acidity (i.e., Brønsted and Lewis). CeO2 benefited from the addition of alkali (Na) or alkaline earth metals (Mg, Ca) by producing unsaturated alcohols.

AB - A series of MeOx-modified CeO2 (CeO2-MnOx, CeO2-ZnO, CeO2-MgO, CeO2-CaO, and CeO2-Na2O) catalysts were prepared by the impregnation of CeO2 with corresponding metal nitrates. Acidity and oxidation state of cerium were investigated on both oxidized and reduced catalysts by employing Fourier Transform Infrared spectroscopy (FTIR) on adsorbed pyridine and in situ H2-Temperature Programmed Reduction/X-ray Absorption Spectroscopy (H2-TPR/XAS) techniques, respectively. Metal oxide addition tended to alter both type and number of acid sites on ceria. EXAFS data showed a significant difference in NCe-O between unmodified and CeO2-MeOx, suggesting that added MeOx interferes with vacancy formation on ceria during reduction. In comparison with air-pretreated samples, H2-pretreated ones under similar conversion of 1,5 pentanediol exhibited a higher selectivity towards linear alcohols. Alcohol conversion found to correlate with total acidity (i.e., Brønsted and Lewis). CeO2 benefited from the addition of alkali (Na) or alkaline earth metals (Mg, Ca) by producing unsaturated alcohols.

KW - 1,5-Pentanediol

KW - Acidity

KW - CeO-MeO

KW - Dehydration

KW - X-ray absorption spectroscopy

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