Changes in Ni-NiO equilibrium due to LaFeO3 and the effect on dry reforming of CH4

Xinyu Mao; Alexandre C. Foucher; Eric A. Stach; Raymond J. Gorte

doi:10.1016/j.jcat.2019.11.040

Changes in Ni-NiO equilibrium due to LaFeO₃ and the effect on dry reforming of CH₄

Xinyu Mao, Alexandre C. Foucher, Eric A. Stach, Raymond J. Gorte

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

36 Scopus citations

Abstract

The interactions between Ni and LaFeO₃ were studied on catalysts prepared by Atomic Layer Deposition (ALD) of 0.5-nm films of LaFeO₃ on MgAl₂O₄. Scanning Transmission Electron Microscopy showed that the films covered the support uniformly, even after 5 redox cycles at 1073 K, and X-Ray Diffraction showed that the films had the perovskite structure. Equilibrium between Ni and NiO was studied using coulometric-titration and flow-titration measurements on 5-wt% Ni catalysts, with and without LaFeO₃. While equilibrium constants for Ni/MgAl₂O₄ were similar to that expected for bulk Ni, equilibrium P_O₂ were shifted to significantly lower values in the presence of LaFeO₃. In studies of Methane Dry Reforming, the shift in equilibrium resulted in catalyst deactivation due to Ni oxidation at low CO:CO₂ ratios, even though Ni/LaFeO₃/MgAl₂O₄ otherwise showed a high reaction rate and excellent tolerance against coking.

Original language	English
Pages (from-to)	561-569
Number of pages	9
Journal	Journal of Catalysis
Volume	381
DOIs	https://doi.org/10.1016/j.jcat.2019.11.040
State	Published - Jan 2020
Externally published	Yes

Funding

This work was funded by the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, Grant No. DE-FG02-13ER16380. The STEM work was carried out in part at the Singh Center for Nanotechnology, part of the National Nanotechnology Coordinated Infrastructure Program, which is supported by the National Science Foundation grant NNCI-1542153. A.C.F. and E.A.S. acknowledge support to Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573. The authors declared that there is no conflict of interest. This work was funded by the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division , Grant No. DE-FG02-13ER16380 . The STEM work was carried out in part at the Singh Center for Nanotechnology, part of the National Nanotechnology Coordinated Infrastructure Program, which is supported by the National Science Foundation grant NNCI-1542153 . A.C.F. and E.A.S. acknowledge support to Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573 .

Funders	Funder number
A.C.F.
Energy Frontier Research Center
IMASC
National Nanotechnology Coordinated Infrastructure Program
Office of Basic Energy Sciences
National Science Foundation	NNCI-1542153
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-SC0012573
College of Science, Technology, Engineering, and Mathematics, Youngstown State University
Chemical Sciences, Geosciences, and Biosciences Division	DE-FG02-13ER16380

Keywords

Atomic Layer Deposition (ALD)
LaFeO
Methane Dry Reforming
Ni-NiO equilibrium
“Intelligent” catalysts

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.jcat.2019.11.040

Cite this

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title = "Changes in Ni-NiO equilibrium due to LaFeO3 and the effect on dry reforming of CH4",

abstract = "The interactions between Ni and LaFeO3 were studied on catalysts prepared by Atomic Layer Deposition (ALD) of 0.5-nm films of LaFeO3 on MgAl2O4. Scanning Transmission Electron Microscopy showed that the films covered the support uniformly, even after 5 redox cycles at 1073 K, and X-Ray Diffraction showed that the films had the perovskite structure. Equilibrium between Ni and NiO was studied using coulometric-titration and flow-titration measurements on 5-wt% Ni catalysts, with and without LaFeO3. While equilibrium constants for Ni/MgAl2O4 were similar to that expected for bulk Ni, equilibrium PO2 were shifted to significantly lower values in the presence of LaFeO3. In studies of Methane Dry Reforming, the shift in equilibrium resulted in catalyst deactivation due to Ni oxidation at low CO:CO2 ratios, even though Ni/LaFeO3/MgAl2O4 otherwise showed a high reaction rate and excellent tolerance against coking.",

keywords = "Atomic Layer Deposition (ALD), LaFeO, Methane Dry Reforming, Ni-NiO equilibrium, “Intelligent” catalysts",

author = "Xinyu Mao and Foucher, {Alexandre C.} and Stach, {Eric A.} and Gorte, {Raymond J.}",

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AU - Mao, Xinyu

AU - Foucher, Alexandre C.

AU - Stach, Eric A.

AU - Gorte, Raymond J.

PY - 2020/1

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N2 - The interactions between Ni and LaFeO3 were studied on catalysts prepared by Atomic Layer Deposition (ALD) of 0.5-nm films of LaFeO3 on MgAl2O4. Scanning Transmission Electron Microscopy showed that the films covered the support uniformly, even after 5 redox cycles at 1073 K, and X-Ray Diffraction showed that the films had the perovskite structure. Equilibrium between Ni and NiO was studied using coulometric-titration and flow-titration measurements on 5-wt% Ni catalysts, with and without LaFeO3. While equilibrium constants for Ni/MgAl2O4 were similar to that expected for bulk Ni, equilibrium PO2 were shifted to significantly lower values in the presence of LaFeO3. In studies of Methane Dry Reforming, the shift in equilibrium resulted in catalyst deactivation due to Ni oxidation at low CO:CO2 ratios, even though Ni/LaFeO3/MgAl2O4 otherwise showed a high reaction rate and excellent tolerance against coking.

AB - The interactions between Ni and LaFeO3 were studied on catalysts prepared by Atomic Layer Deposition (ALD) of 0.5-nm films of LaFeO3 on MgAl2O4. Scanning Transmission Electron Microscopy showed that the films covered the support uniformly, even after 5 redox cycles at 1073 K, and X-Ray Diffraction showed that the films had the perovskite structure. Equilibrium between Ni and NiO was studied using coulometric-titration and flow-titration measurements on 5-wt% Ni catalysts, with and without LaFeO3. While equilibrium constants for Ni/MgAl2O4 were similar to that expected for bulk Ni, equilibrium PO2 were shifted to significantly lower values in the presence of LaFeO3. In studies of Methane Dry Reforming, the shift in equilibrium resulted in catalyst deactivation due to Ni oxidation at low CO:CO2 ratios, even though Ni/LaFeO3/MgAl2O4 otherwise showed a high reaction rate and excellent tolerance against coking.

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