Effect of altervalent cation-doping on catalytic activity of neodymium sesquioxide for oxidative coupling of methane

Sung Han Lee, Da Woon Jung, Jung Bae Kim, Yong Rok Kim

Research output: Contribution to journalArticle

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Abstract

Altervalent cation-doped neodymium sesquioxide systems such as Ni/Nd2O3, Mn/Nd2O3, and Zr/Nd2O3 with various doping mole fractions were prepared and the cation-doping effect on the catalytic activity of neodymium oxide in the oxidative coupling of methane was investigated. The catalytic reaction was carried out in a flow reactor system using on-line gas chromatography. The reaction conditions were 550-800°C, feed mole ratio of CH4/O2/He=6/1/5, total feed flow rate=30.0 cm3 min-1, and 1 atm of pressure. The present catalysts were effective for the oxidative coupling of methane, the selectivity to higher hydrocarbons was increased by doping the cations into Nd2O3. Among the catalysts tested, 5 mol% Zr-doped Nd2O3 showed the best Cn-selectivity (n≥2) of 74.1% with a yield of 13.0% at 750°C. Pure Nd2O3, Ni-doped Nd2O3, and Mn-doped Nd2O3 catalysts showed no C3-hydrocarbon product selectivity, while Zr-doped Nd2O3 catalysts showed C3-hydrocarbon product selectivity ranging from 6% to 12%. When the oxygen-pretreated 5 mol% Ni-doped Nd2O3 catalyst was exposed to CH4 at 400°C, a detectable amount of H2 was produced, indicating that CH4 can be selectively activated by oxygen species on the surface. The formation of interstitial oxygen ions through the reaction of oxygen with the oxide is a controlling factor for the catalytic activity of the oxide in the oxidative coupling of methane. The oxygen vacancy formed by doping divalent cation into Nd2O3 exerts influence on the formation of active oxygen ion. Zr4+-doping can also increase the concentration of active oxygen ion in the oxide. Defects and active sites in the catalyst are discussed on the basis of solid-state chemistry.

Original languageEnglish
Pages (from-to)159-169
Number of pages11
JournalApplied Catalysis A: General
Volume164
Issue number1-2
DOIs
Publication statusPublished - 1997 Dec 23

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Neodymium
Methane
Cations
Catalyst activity
Positive ions
Doping (additives)
Catalysts
Oxygen
Oxides
Catalyst selectivity
Hydrocarbons
Ions
Online systems
Oxygen vacancies
Gas chromatography
neodymium oxide
Reactive Oxygen Species
Flow rate
Defects
Divalent Cations

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Process Chemistry and Technology

Cite this

@article{ea3a8061189a489585fa34469944b019,
title = "Effect of altervalent cation-doping on catalytic activity of neodymium sesquioxide for oxidative coupling of methane",
abstract = "Altervalent cation-doped neodymium sesquioxide systems such as Ni/Nd2O3, Mn/Nd2O3, and Zr/Nd2O3 with various doping mole fractions were prepared and the cation-doping effect on the catalytic activity of neodymium oxide in the oxidative coupling of methane was investigated. The catalytic reaction was carried out in a flow reactor system using on-line gas chromatography. The reaction conditions were 550-800°C, feed mole ratio of CH4/O2/He=6/1/5, total feed flow rate=30.0 cm3 min-1, and 1 atm of pressure. The present catalysts were effective for the oxidative coupling of methane, the selectivity to higher hydrocarbons was increased by doping the cations into Nd2O3. Among the catalysts tested, 5 mol{\%} Zr-doped Nd2O3 showed the best Cn-selectivity (n≥2) of 74.1{\%} with a yield of 13.0{\%} at 750°C. Pure Nd2O3, Ni-doped Nd2O3, and Mn-doped Nd2O3 catalysts showed no C3-hydrocarbon product selectivity, while Zr-doped Nd2O3 catalysts showed C3-hydrocarbon product selectivity ranging from 6{\%} to 12{\%}. When the oxygen-pretreated 5 mol{\%} Ni-doped Nd2O3 catalyst was exposed to CH4 at 400°C, a detectable amount of H2 was produced, indicating that CH4 can be selectively activated by oxygen species on the surface. The formation of interstitial oxygen ions through the reaction of oxygen with the oxide is a controlling factor for the catalytic activity of the oxide in the oxidative coupling of methane. The oxygen vacancy formed by doping divalent cation into Nd2O3 exerts influence on the formation of active oxygen ion. Zr4+-doping can also increase the concentration of active oxygen ion in the oxide. Defects and active sites in the catalyst are discussed on the basis of solid-state chemistry.",
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Effect of altervalent cation-doping on catalytic activity of neodymium sesquioxide for oxidative coupling of methane. / Lee, Sung Han; Jung, Da Woon; Kim, Jung Bae; Kim, Yong Rok.

In: Applied Catalysis A: General, Vol. 164, No. 1-2, 23.12.1997, p. 159-169.

Research output: Contribution to journalArticle

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T1 - Effect of altervalent cation-doping on catalytic activity of neodymium sesquioxide for oxidative coupling of methane

AU - Lee, Sung Han

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N2 - Altervalent cation-doped neodymium sesquioxide systems such as Ni/Nd2O3, Mn/Nd2O3, and Zr/Nd2O3 with various doping mole fractions were prepared and the cation-doping effect on the catalytic activity of neodymium oxide in the oxidative coupling of methane was investigated. The catalytic reaction was carried out in a flow reactor system using on-line gas chromatography. The reaction conditions were 550-800°C, feed mole ratio of CH4/O2/He=6/1/5, total feed flow rate=30.0 cm3 min-1, and 1 atm of pressure. The present catalysts were effective for the oxidative coupling of methane, the selectivity to higher hydrocarbons was increased by doping the cations into Nd2O3. Among the catalysts tested, 5 mol% Zr-doped Nd2O3 showed the best Cn-selectivity (n≥2) of 74.1% with a yield of 13.0% at 750°C. Pure Nd2O3, Ni-doped Nd2O3, and Mn-doped Nd2O3 catalysts showed no C3-hydrocarbon product selectivity, while Zr-doped Nd2O3 catalysts showed C3-hydrocarbon product selectivity ranging from 6% to 12%. When the oxygen-pretreated 5 mol% Ni-doped Nd2O3 catalyst was exposed to CH4 at 400°C, a detectable amount of H2 was produced, indicating that CH4 can be selectively activated by oxygen species on the surface. The formation of interstitial oxygen ions through the reaction of oxygen with the oxide is a controlling factor for the catalytic activity of the oxide in the oxidative coupling of methane. The oxygen vacancy formed by doping divalent cation into Nd2O3 exerts influence on the formation of active oxygen ion. Zr4+-doping can also increase the concentration of active oxygen ion in the oxide. Defects and active sites in the catalyst are discussed on the basis of solid-state chemistry.

AB - Altervalent cation-doped neodymium sesquioxide systems such as Ni/Nd2O3, Mn/Nd2O3, and Zr/Nd2O3 with various doping mole fractions were prepared and the cation-doping effect on the catalytic activity of neodymium oxide in the oxidative coupling of methane was investigated. The catalytic reaction was carried out in a flow reactor system using on-line gas chromatography. The reaction conditions were 550-800°C, feed mole ratio of CH4/O2/He=6/1/5, total feed flow rate=30.0 cm3 min-1, and 1 atm of pressure. The present catalysts were effective for the oxidative coupling of methane, the selectivity to higher hydrocarbons was increased by doping the cations into Nd2O3. Among the catalysts tested, 5 mol% Zr-doped Nd2O3 showed the best Cn-selectivity (n≥2) of 74.1% with a yield of 13.0% at 750°C. Pure Nd2O3, Ni-doped Nd2O3, and Mn-doped Nd2O3 catalysts showed no C3-hydrocarbon product selectivity, while Zr-doped Nd2O3 catalysts showed C3-hydrocarbon product selectivity ranging from 6% to 12%. When the oxygen-pretreated 5 mol% Ni-doped Nd2O3 catalyst was exposed to CH4 at 400°C, a detectable amount of H2 was produced, indicating that CH4 can be selectively activated by oxygen species on the surface. The formation of interstitial oxygen ions through the reaction of oxygen with the oxide is a controlling factor for the catalytic activity of the oxide in the oxidative coupling of methane. The oxygen vacancy formed by doping divalent cation into Nd2O3 exerts influence on the formation of active oxygen ion. Zr4+-doping can also increase the concentration of active oxygen ion in the oxide. Defects and active sites in the catalyst are discussed on the basis of solid-state chemistry.

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