Abstract
Catalytic descriptors were studied to design optimum catalysts for the oxidative coupling of methane (OCM) by combining density functional theory (DFT) calculations and actual reaction experiments. SrTiO3 perovskite catalysts, selected for OCM, were modified using metal dopants, and their electronic structures were calculated using the DFT method. The CH3 adsorption energy Eads(CH3) and the oxygen vacancy formation energy Ef(vac) exhibited volcano-type correlations with the C2+ selectivity and O2-consumption for the formation of COx, respectively. The optimum catalytic activity, represented by the C2+ selectivity, was obtained for Eads(CH3) = −2.0 to −1.5 eV, indicating that overly strong adsorption of methyl radicals (or easily dissociated C[sbnd]H bonds of methane) and relatively insufficient oxygen supplementation to the catalyst surface improve deep oxidation to CO and CO2. Praseodymium (Pr)- and neodymium (Nd)-doped SrTiO3 catalysts confirm the DFT-predicted optimum electronic structure of the OCM catalysts.
| Original language | English |
|---|---|
| Pages (from-to) | 478-492 |
| Number of pages | 15 |
| Journal | Journal of Catalysis |
| Volume | 375 |
| DOIs | |
| Publication status | Published - 2019 Jul 1 |
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Keywords
- Density functional theory
- Methyl radical adsorption
- Oxidative coupling of methane
- Perovskite
ASJC Scopus subject areas
- Catalysis
- Physical and Theoretical Chemistry
Cite this
Combined experimental and density functional theory (DFT) studies on the catalyst design for the oxidative coupling of methane. / Lim, Seoyeon; Choi, Jae Wook; Suh, Dong Jin; Song, Kwang Ho; Ham, Hyung Chul; Ha, Jeong Myeong.
In: Journal of Catalysis, Vol. 375, 01.07.2019, p. 478-492.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Combined experimental and density functional theory (DFT) studies on the catalyst design for the oxidative coupling of methane
AU - Lim, Seoyeon
AU - Choi, Jae Wook
AU - Suh, Dong Jin
AU - Song, Kwang Ho
AU - Ham, Hyung Chul
AU - Ha, Jeong Myeong
PY - 2019/7/1
Y1 - 2019/7/1
N2 - Catalytic descriptors were studied to design optimum catalysts for the oxidative coupling of methane (OCM) by combining density functional theory (DFT) calculations and actual reaction experiments. SrTiO3 perovskite catalysts, selected for OCM, were modified using metal dopants, and their electronic structures were calculated using the DFT method. The CH3 adsorption energy Eads(CH3) and the oxygen vacancy formation energy Ef(vac) exhibited volcano-type correlations with the C2+ selectivity and O2-consumption for the formation of COx, respectively. The optimum catalytic activity, represented by the C2+ selectivity, was obtained for Eads(CH3) = −2.0 to −1.5 eV, indicating that overly strong adsorption of methyl radicals (or easily dissociated C[sbnd]H bonds of methane) and relatively insufficient oxygen supplementation to the catalyst surface improve deep oxidation to CO and CO2. Praseodymium (Pr)- and neodymium (Nd)-doped SrTiO3 catalysts confirm the DFT-predicted optimum electronic structure of the OCM catalysts.
AB - Catalytic descriptors were studied to design optimum catalysts for the oxidative coupling of methane (OCM) by combining density functional theory (DFT) calculations and actual reaction experiments. SrTiO3 perovskite catalysts, selected for OCM, were modified using metal dopants, and their electronic structures were calculated using the DFT method. The CH3 adsorption energy Eads(CH3) and the oxygen vacancy formation energy Ef(vac) exhibited volcano-type correlations with the C2+ selectivity and O2-consumption for the formation of COx, respectively. The optimum catalytic activity, represented by the C2+ selectivity, was obtained for Eads(CH3) = −2.0 to −1.5 eV, indicating that overly strong adsorption of methyl radicals (or easily dissociated C[sbnd]H bonds of methane) and relatively insufficient oxygen supplementation to the catalyst surface improve deep oxidation to CO and CO2. Praseodymium (Pr)- and neodymium (Nd)-doped SrTiO3 catalysts confirm the DFT-predicted optimum electronic structure of the OCM catalysts.
KW - Density functional theory
KW - Methyl radical adsorption
KW - Oxidative coupling of methane
KW - Perovskite
UR - http://www.scopus.com/inward/record.url?scp=85068550811&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85068550811&partnerID=8YFLogxK
U2 - 10.1016/j.jcat.2019.04.008
DO - 10.1016/j.jcat.2019.04.008
M3 - Article
AN - SCOPUS:85068550811
VL - 375
SP - 478
EP - 492
JO - Journal of Catalysis
JF - Journal of Catalysis
SN - 0021-9517
ER -