A thermodynamic investigation of ni on thin-film titanates (Atio3)

Chao Lin; Alexandre C. Foucher; Eric A. Stach; Raymond J. Gorte

doi:10.3390/inorganics8120069

A thermodynamic investigation of ni on thin-film titanates (Atio₃)

Chao Lin
, Alexandre C. Foucher
, Eric A. Stach
, Raymond J. Gorte

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

9 Scopus citations

Abstract

Thin, ~1-nm films of CaTiO₃, SrTiO₃, and BaTiO₃ were deposited onto MgAl₂O₄ by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl₂O₄, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower P_O2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO₃, followed by SrTiO₃ and BaTiO₃. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO₃ /MgAl₂O₄ catalyst for CO₂ reforming of CH₄ at high CO₂ pressures, due to the oxidation of the Ni.

Original language	English
Article number	69
Pages (from-to)	1-13
Number of pages	13
Journal	Inorganics
Volume	8
Issue number	12
DOIs	https://doi.org/10.3390/inorganics8120069
State	Published - Dec 2020
Externally published	Yes

Funding

This research was funded by Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, Grant No. DE-FG02-13ER16380. This work was performed in part at the Singh Center for Nanotechnology at the University of Pennsylvania, a member of the National Nanotechnology Coordinated Infrastructure (NNCI) network, which is supported by the National Science Foundation (Grant NNCI-1542153). Acknowledgments: C.L. and R.J.G. are grateful to the Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, Grant No. DE-FG02-13ER16380 for support of this work. A.C.F and E.A.S. acknowledge support for a Fellowship to A.C.F. from the Vagelos Institute for Energy Science and Technology at the University of Pennsylvania. The authors gratefully acknowledge use of facilities and instrumentation supported by NSF through the University of Pennsylvania Materials Research Science and Engineering Center (MRSEC) (DMR-1720530). Funding: This research was funded by Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, Grant No. DE-FG02-13ER16380. This work was performed in part at the Singh Center for Nanotechnology at the University of Pennsylvania, a member of the National Nanotechnology Coordinated Infrastructure (NNCI) network, which is supported by the National Science Foundation (Grant NNCI-1542153).

Keywords

Atomic Layer Deposition
Ni catalyst
Reforming catalyst
Thermodynamics

Access to Document

10.3390/inorganics8120069

Cite this

@article{f921bf7cd755480a827dede0d462dba3,

title = "A thermodynamic investigation of ni on thin-film titanates (Atio3)",

abstract = "Thin, \textasciitilde{}1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for \textasciitilde{}5 wt \% of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO3 /MgAl2O4 catalyst for CO2 reforming of CH4 at high CO2 pressures, due to the oxidation of the Ni.",

keywords = "Atomic Layer Deposition, Ni catalyst, Reforming catalyst, Thermodynamics",

author = "Chao Lin and Foucher, \{Alexandre C.\} and Stach, \{Eric A.\} and Gorte, \{Raymond J.\}",

note = "Publisher Copyright: {\textcopyright} 2020 by the authors. Licensee MDPI, Basel, Switzerland.",

year = "2020",

month = dec,

doi = "10.3390/inorganics8120069",

language = "English",

volume = "8",

pages = "1--13",

journal = "Inorganics",

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T1 - A thermodynamic investigation of ni on thin-film titanates (Atio3)

AU - Lin, Chao

AU - Foucher, Alexandre C.

AU - Stach, Eric A.

AU - Gorte, Raymond J.

PY - 2020/12

Y1 - 2020/12

N2 - Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO3 /MgAl2O4 catalyst for CO2 reforming of CH4 at high CO2 pressures, due to the oxidation of the Ni.

AB - Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO3 /MgAl2O4 catalyst for CO2 reforming of CH4 at high CO2 pressures, due to the oxidation of the Ni.

KW - Atomic Layer Deposition

KW - Ni catalyst

KW - Reforming catalyst

KW - Thermodynamics

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DO - 10.3390/inorganics8120069

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