Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach
Abstract
Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1657295
- Alternate Identifier(s):
- OSTI ID: 1756367
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Catalysts
- Additional Journal Information:
- Journal Name: Catalysts Journal Volume: 10 Journal Issue: 9; Journal ID: ISSN 2073-4344
- Publisher:
- MDPI
- Country of Publication:
- Switzerland
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; palladium carbide; graphite; metal-support interaction; coking; palladium-zirconium intermetallic phase; in-situ X-ray photoelectron spectroscopy; in-situ X-ray diffraction; high resolution electron microscopy; dry reforming of methane; carbon dioxide activation
Citation Formats
Köpfle, Norbert, Ploner, Kevin, Lackner, Peter, Götsch, Thomas, Thurner, Christoph, Carbonio, Emilia, Hävecker, Michael, Knop-Gericke, Axel, Schlicker, Lukas, Doran, Andrew, Kober, Delf, Gurlo, Aleksander, Willinger, Marc, Penner, Simon, Schmid, Michael, and Klötzer, Bernhard. Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach. Switzerland: N. p., 2020.
Web. doi:10.3390/catal10091000.
Köpfle, Norbert, Ploner, Kevin, Lackner, Peter, Götsch, Thomas, Thurner, Christoph, Carbonio, Emilia, Hävecker, Michael, Knop-Gericke, Axel, Schlicker, Lukas, Doran, Andrew, Kober, Delf, Gurlo, Aleksander, Willinger, Marc, Penner, Simon, Schmid, Michael, & Klötzer, Bernhard. Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach. Switzerland. https://doi.org/10.3390/catal10091000
Köpfle, Norbert, Ploner, Kevin, Lackner, Peter, Götsch, Thomas, Thurner, Christoph, Carbonio, Emilia, Hävecker, Michael, Knop-Gericke, Axel, Schlicker, Lukas, Doran, Andrew, Kober, Delf, Gurlo, Aleksander, Willinger, Marc, Penner, Simon, Schmid, Michael, and Klötzer, Bernhard. Wed .
"Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach". Switzerland. https://doi.org/10.3390/catal10091000.
@article{osti_1657295,
title = {Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach},
author = {Köpfle, Norbert and Ploner, Kevin and Lackner, Peter and Götsch, Thomas and Thurner, Christoph and Carbonio, Emilia and Hävecker, Michael and Knop-Gericke, Axel and Schlicker, Lukas and Doran, Andrew and Kober, Delf and Gurlo, Aleksander and Willinger, Marc and Penner, Simon and Schmid, Michael and Klötzer, Bernhard},
abstractNote = {Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.},
doi = {10.3390/catal10091000},
journal = {Catalysts},
number = 9,
volume = 10,
place = {Switzerland},
year = {Wed Sep 02 00:00:00 EDT 2020},
month = {Wed Sep 02 00:00:00 EDT 2020}
}
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Works referenced in this record:
Perovskites as Precursors for Ni/La 2 O 3 Catalysts in the Dry Reforming of Methane: Synthesis by Constant pH Co-Precipitation, Reduction Mechanism and Effect of Ru-Doping: Perovskites as Precursors for Ni/La2O3 Catalysts in the Dry Reforming of Methane: Synthesis by Constant pH Co-Precipitation, Reduction Mechanism and E
journal, July 2017
- Kühl, Stefanie; Düdder, Hendrik; Girgsdies, Frank
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 643, Issue 16
Catalytic reactions of hydrocarbon with carbon dioxide over metallic catalysts
journal, September 1984
- Sakai, Y.; Saito, H.; Sodesawa, T.
- Reaction Kinetics and Catalysis Letters, Vol. 24, Issue 3-4
Surface and subsurface alloy formation of vanadium on Pd(111)
journal, September 2000
- Konvicka, Ch.; Jeanvoine, Y.; Lundgren, E.
- Surface Science, Vol. 463, Issue 3
Intrinsic reactivity of Ni, Pd and Pt surfaces in dry reforming and competitive reactions: Insights from first principles calculations and microkinetic modeling simulations
journal, November 2016
- Foppa, Lucas; Silaghi, Marius-Christian; Larmier, Kim
- Journal of Catalysis, Vol. 343
Transmission in situ and operando high temperature X-ray powder diffraction in variable gaseous environments
journal, March 2018
- Schlicker, Lukas; Doran, Andrew; Schneppmüller, Peter
- Review of Scientific Instruments, Vol. 89, Issue 3
The role of catalyst support on the activity of nickel for reforming methane with CO2
journal, January 1988
- Gadalla, Ahmed M.; Bower, Barbara
- Chemical Engineering Science, Vol. 43, Issue 11
Effect of support composition on the origin and reactivity of carbon formed during dry reforming of methane over 5wt% Ni/Ce1−xMxO2−δ (M=Zr4+, Pr3+) catalysts
journal, January 2016
- Makri, M. M.; Vasiliades, M. A.; Petallidou, K. C.
- Catalysis Today, Vol. 259
Review on Innovative Catalytic Reforming of Natural Gas to Syngas
journal, January 2016
- Ghoneim, Salwa A.; El-Salamony, Radwa A.; El-Temtamy, Seham A.
- World Journal of Engineering and Technology, Vol. 04, Issue 01
The Enthalpy Effect on Forming Diluted Solid Solutions of Two 4d and 5d Transition Metals
journal, September 1983
- Niessen, Anton K.; Miedema, Andries R.
- Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 87, Issue 9
Surface modification processes during methane decomposition on Cu-promoted Ni–ZrO 2 catalysts
journal, January 2015
- Wolfbeisser, Astrid; Klötzer, Bernhard; Mayr, Lukas
- Catalysis Science & Technology, Vol. 5, Issue 2
Electron spectroscopic identification of carbon species formed during diamond growth
journal, May 1990
- Belton, David N.; Schmieg, Steven J.
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 8, Issue 3
Catalytic Dry Reforming of Methane: Insights from Model Systems
journal, February 2020
- Wittich, Knut; Krämer, Michael; Bottke, Nils
- ChemCatChem, Vol. 12, Issue 8
Growth of an Ultrathin Zirconia Film on Pt 3 Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory
journal, January 2015
- Li, Hao; Choi, Joong-Il Jake; Mayr-Schmölzer, Wernfried
- The Journal of Physical Chemistry C
Dynamical Properties of a Ru/MgAl 2 O 4 Catalyst during Reduction and Dry Methane Reforming
journal, September 2012
- Kehres, Jan; Jakobsen, Jon Geest; Andreasen, Jens Wenzel
- The Journal of Physical Chemistry C, Vol. 116, Issue 40
Mono and Bifunctional Pathways of CO2/CH4Reforming over Pt and Rh Based Catalysts
journal, May 1998
- Bitter, J. H.; Seshan, K.; Lercher, J. A.
- Journal of Catalysis, Vol. 176, Issue 1
Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO 2 Electrolysis Investigated by Operando Photoelectron Spectroscopy
journal, October 2017
- Opitz, Alexander K.; Nenning, Andreas; Rameshan, Christoph
- ACS Applied Materials & Interfaces, Vol. 9, Issue 41
Substoichiometric ultrathin zirconia films cause strong metal–support interaction
journal, January 2019
- Lackner, Peter; Choi, Joong Il Jake; Diebold, Ulrike
- Journal of Materials Chemistry A, Vol. 7, Issue 43
Catalytic reforming of methane with carbon dioxide over nickel catalysts I. Catalyst characterization and activity
journal, August 1996
- Bradford, Michael C. J.; Vannice, M. Albert
- Applied Catalysis A: General, Vol. 142, Issue 1
Development of Ni-Pd bimetallic catalysts for the utilization of carbon dioxide and methane by dry reforming
journal, September 2009
- Steinhauer, Bernd; Kasireddy, Mohan Reddy; Radnik, Jörg
- Applied Catalysis A: General, Vol. 366, Issue 2
In Situ-Determined Catalytically Active State of LaNiO 3 in Methane Dry Reforming
journal, December 2019
- Bonmassar, Nicolas; Bekheet, Maged F.; Schlicker, Lukas
- ACS Catalysis, Vol. 10, Issue 2
Pt Zr(0001): A substrate for growing well-ordered ultrathin zirconia films by oxidation
journal, July 2012
- Antlanger, Moritz; Mayr-Schmölzer, Wernfried; Pavelec, Jiří
- Physical Review B, Vol. 86, Issue 3
A Transient Kinetic Study of the Carbon Dioxide Reforming of Methane over Supported Ru Catalysts
journal, May 1999
- Ferreira-Aparicio, P.; Márquez-Alvarez, C.; Rodrı́guez-Ramos, I.
- Journal of Catalysis, Vol. 184, Issue 1
In situ NAP-XPS spectroscopy during methane dry reforming on ZrO 2 /Pt(1 1 1) inverse model catalyst
journal, June 2018
- Rameshan, C.; Li, H.; Anic, K.
- Journal of Physics: Condensed Matter, Vol. 30, Issue 26
The State of Zirconia Supported Platinum Catalysts for CO2/CH4Reforming
journal, October 1997
- Bitter, J. H.; Seshan, K.; Lercher, J. A.
- Journal of Catalysis, Vol. 171, Issue 1
A review on coke management during dry reforming of methane: Revisiting coke management in dry reforming of methane
journal, January 2015
- Muraza, Oki; Galadima, Ahmad
- International Journal of Energy Research, Vol. 39, Issue 9
Reversible formation of a PdCx phase in Pd nanoparticles upon CO and O2 exposure
journal, January 2012
- Balmes, Olivier; Resta, Andrea; Wermeille, Didier
- Physical Chemistry Chemical Physics, Vol. 14, Issue 14
Contrasting the Role of Ni/Al 2 O 3 Interfaces in Water–Gas Shift and Dry Reforming of Methane
journal, November 2017
- Foppa, Lucas; Margossian, Tigran; Kim, Sung Min
- Journal of the American Chemical Society, Vol. 139, Issue 47
Isotopic and kinetic assessment of the mechanism of reactions of CH4 with CO2 or H2O to form synthesis gas and carbon on nickel catalysts
journal, June 2004
- Wei, Junmei; Iglesia, Enrique
- Journal of Catalysis, Vol. 224, Issue 2
X-Ray Photoelectron Spectroscopic Studies of Palladium Dispersed on Carbon Surfaces Modified by Ion Beams and Plasmatic Oxidation
journal, January 1995
- Bastl, Zdeněk
- Collection of Czechoslovak Chemical Communications, Vol. 60, Issue 3
Using photoelectron spectroscopy to observe oxygen spillover to zirconia
journal, January 2019
- Lackner, Peter; Zou, Zhiyu; Mayr, Sabrina
- Physical Chemistry Chemical Physics, Vol. 21, Issue 32
CO adsorption on supported Pd catalysts studied by adsorption microcalorimetry and temperature programmed desorption
journal, September 1997
- Dropsch, Holger; Baerns, Manfred
- Applied Catalysis A: General, Vol. 158, Issue 1-2
Development of stable bimetallic catalysts for carbon dioxide reforming of methane
journal, July 2007
- Zhang, J.; Wang, H.; Dalai, A.
- Journal of Catalysis, Vol. 249, Issue 2
Zirconium-Palladium Interactions during Dry Reforming of Methane
journal, May 2017
- Köpfle, Norbert; Mayr, Lukas; Lackner, Peter
- ECS Transactions, Vol. 78, Issue 1
Role of Precursor Carbides for Graphene Growth on Ni(111)
journal, February 2018
- Rameshan, Raffael; Vonk, Vedran; Franz, Dirk
- Scientific Reports, Vol. 8, Issue 1
Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts
journal, April 2010
- Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli
- Nature Chemistry, Vol. 2, Issue 6
Catalytic Technology for Carbon Dioxide Reforming of Methane to Synthesis Gas
journal, October 2009
- Fan, Mun-Sing; Abdullah, Ahmad Zuhairi; Bhatia, Subhash
- ChemCatChem, Vol. 1, Issue 2
In situ XPS study of Pd(111) oxidation at elevated pressure, Part 2: Palladium oxidation in the 10−1mbar range
journal, August 2006
- Gabasch, Harald; Unterberger, Werner; Hayek, Konrad
- Surface Science, Vol. 600, Issue 15
Dry reforming of methane has no future for hydrogen production: Comparison with steam reforming at high pressure in standard and membrane reactors
journal, July 2012
- Oyama, S. Ted; Hacarlioglu, Pelin; Gu, Yunfeng
- International Journal of Hydrogen Energy, Vol. 37, Issue 13
The growth of ultra-thin zirconia films on Pd 3 Zr(0 0 0 1)
journal, May 2014
- Choi, J. I. J.; Mayr-Schmölzer, W.; Mittendorfer, F.
- Journal of Physics: Condensed Matter, Vol. 26, Issue 22
Alcohol synthesis from syngas
journal, October 1993
- Alyea, Elm C.; He, Dasen; Wang, Jueh
- Applied Catalysis A: General, Vol. 104, Issue 1
Pd–Au bimetallic catalysts: understanding alloy effects from planar models and (supported) nanoparticles
journal, January 2012
- Gao, Feng; Goodman, D. Wayne
- Chemical Society Reviews, Vol. 41, Issue 24
Partial oxidation of methane to synthesis gas using carbon dioxide
journal, July 1991
- Ashcroft, A. T.; Cheetham, A. K.; Green, M. L. H.
- Nature, Vol. 352, Issue 6332
Carbon Dioxide Reforming of Methane To Produce Synthesis Gas over Metal-Supported Catalysts: State of the Art
journal, January 1996
- Wang, Shaobin; Lu, G. Q. (Max); Millar, Graeme J.
- Energy & Fuels, Vol. 10, Issue 4
Hydrogenolysis of CFC-12 (CF2Cl2) over Pd/γ-Al2O3 pretreated with HCFC-22 (CHF2Cl)
journal, February 2000
- Ahn, Byoung Sung; Jeon, Sang Goo; Lee, Hyunjoo
- Applied Catalysis A: General, Vol. 193, Issue 1-2
Methane dry reforming over ceria-zirconia supported Ni catalysts
journal, November 2016
- Wolfbeisser, Astrid; Sophiphun, Onsulang; Bernardi, Johannes
- Catalysis Today, Vol. 277
In Situ X-Ray Photoelectron Spectroscopy Studies of Gas-Solid Interfaces at Near-Ambient Conditions
journal, December 2007
- Bluhm, Hendrik; Hävecker, Michael; Knop-Gericke, Axel
- MRS Bulletin, Vol. 32, Issue 12
Carbon dioxide reforming of methane over La2NiO4 as catalyst precursor—Characterization of carbon deposition
journal, April 2008
- Sierra Gallego, Germán; Mondragón, Fanor; Tatibouët, Jean-Michel
- Catalysis Today, Vol. 133-135
Surface Reactivity of YSZ, Y 2 O 3 , and ZrO 2 toward CO, CO 2 , and CH 4 : A Comparative Discussion
journal, February 2016
- Kogler, Michaela; Köck, Eva-Maria; Klötzer, Bernhard
- The Journal of Physical Chemistry C, Vol. 120, Issue 7
Water adsorption at zirconia: from the ZrO 2 (111)/Pt 3 Zr(0001) model system to powder samples
journal, January 2018
- Lackner, Peter; Hulva, Jan; Köck, Eva-Maria
- Journal of Materials Chemistry A, Vol. 6, Issue 36
CO 2 Reforming of CH 4
journal, February 1999
- Bradford, M. C. J.; Vannice, M. A.
- Catalysis Reviews, Vol. 41, Issue 1
The Roles of Subsurface Carbon and Hydrogen in Palladium-Catalyzed Alkyne Hydrogenation
journal, April 2008
- Teschner, D.; Borsodi, J.; Wootsch, A.
- Science, Vol. 320, Issue 5872
Compact low power infrared tube furnace for in situ X-ray powder diffraction
journal, January 2017
- Doran, A.; Schlicker, L.; Beavers, C. M.
- Review of Scientific Instruments, Vol. 88, Issue 1
Ligand and ensemble effects in adsorption on alloy surfaces
journal, January 2001
- Liu, P.; Nørskov, J. K.
- Physical Chemistry Chemical Physics, Vol. 3, Issue 17
Dry Reforming of Methane Over Cobalt Catalysts: A Literature Review of Catalyst Development
journal, September 2012
- Budiman, Anatta Wahyu; Song, Sang-Hoon; Chang, Tae-Sun
- Catalysis Surveys from Asia, Vol. 16, Issue 4
CO 2 Reduction on the Pre-reduced Mixed Ionic-Electronic Conducting Perovskites La 0.6 Sr -0.4 FeO 3-δ and SrTi 0.7 Fe 0.3 O 3-δ
journal, November 2017
- Grünbacher, Matthias; Götsch, Thomas; Opitz, Alexander K.
- ChemPhysChem, Vol. 19, Issue 1
Incorporation of carbon into palladium during low-temperature disproportionation of carbon monoxide over palladium/zirconia prepared from glassy palladium-zirconium
journal, January 1994
- Maciejewski, M.; Baiker, A.
- The Journal of Physical Chemistry, Vol. 98, Issue 1
Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts
journal, May 2014
- Mayr, Lukas; Rameshan, Raffael; Klötzer, Bernhard
- Review of Scientific Instruments, Vol. 85, Issue 5
Pulse Microcalorimetry Study of Methane Dry Reforming Reaction on Ni/Ceria-Zirconia Catalyst
journal, September 2017
- Simonov, Mikhail; Rogov, Vladimir; Smirnova, Marina
- Catalysts, Vol. 7, Issue 9
Zirconium-Assisted Activation of Palladium To Boost Syngas Production by Methane Dry Reforming
journal, September 2018
- Köpfle, Norbert; Götsch, Thomas; Grünbacher, Matthias
- Angewandte Chemie International Edition, Vol. 57, Issue 44
XPS, EM, and Catalytic Studies of the Accumulation of Carbon on Pt Black
journal, January 2001
- Rodriguez, N. M.; Anderson, P. E.; Wootsch, A.
- Journal of Catalysis, Vol. 197, Issue 2
Catalytic reaction of CH4 with CO2 over alumina-supported Pt metals
journal, January 1991
- Solymosi, F.; Kuts�n, Gy.; Erd�helyi, A.
- Catalysis Letters, Vol. 11, Issue 2
A review of dry (CO 2 ) reforming of methane over noble metal catalysts
journal, January 2014
- Pakhare, Devendra; Spivey, James
- Chem. Soc. Rev., Vol. 43, Issue 22
A Comparative Discussion of the Catalytic Activity and CO2-Selectivity of Cu-Zr and Pd-Zr (Intermetallic) Compounds in Methanol Steam Reforming
journal, February 2017
- Köpfle, Norbert; Mayr, Lukas; Schmidmair, Daniela
- Catalysts, Vol. 7, Issue 12
The effect of CeO2 on the surface and catalytic properties of Pt/CeO2–ZrO2 catalysts for methane dry reforming
journal, July 2009
- Damyanova, S.; Pawelec, B.; Arishtirova, K.
- Applied Catalysis B: Environmental, Vol. 89, Issue 1-2
Carbon dioxide reforming of methane over glow discharge plasma-reduced Ir/Al2O3 catalyst
journal, April 2008
- Zhao, Yu; Pan, Yun-xiang; Xie, Yongbing
- Catalysis Communications, Vol. 9, Issue 7
CO2-Reforming of Methane over Transition Metals
journal, November 1993
- Rostrupnielsen, J. R.; Hansen, J. H. B.
- Journal of Catalysis, Vol. 144, Issue 1
Dry reforming of methane in membrane reactors using Pd and Pd–Ag composite membranes on a NaA zeolite modified porous stainless steel support
journal, November 2010
- Bosko, M. L.; Múnera, J. F.; Lombardo, E. A.
- Journal of Membrane Science, Vol. 364, Issue 1-2
Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996
- Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
- High Pressure Research, Vol. 14, Issue 4-6, p. 235-248