In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

Handle URI:
http://hdl.handle.net/10754/623410
Title:
In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction
Authors:
Al-Sabban, Bedour ( 0000-0002-9036-9957 ) ; Falivene, Laura ( 0000-0003-1509-6191 ) ; Kozlov, Sergey M.; Aguilar Tapia, Antonio; Ould-Chikh, Samy ( 0000-0002-3486-0944 ) ; Hazemann, Jean-Louis; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Basset, Jean-Marie ( 0000-0003-3166-8882 ) ; Takanabe, Kazuhiro ( 0000-0001-5374-9451 )
Abstract:
Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals Co and Ni, which have high affinity with CO2 and high activity for CH4 decomposition, respectively. This study was focused on providing evidence of the capturing surface coverage of the reactive intermediates and the associated structural changes of the metals during DRM at high temperature using in-operando X-ray absorption spectroscopy (XAS). On the Co catalysts, the first-order effects with respect to CH4 pressure and negative-order effects with respect to CO2 pressure on the DRM rate are consistent with the competitive adsorption of the surface oxygen species on the same sites as the CH4 decomposition reaction. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst exhibits reactivity towards the DRM but with kinetic orders resembling Co catalyst, producing negligible carbon deposition by balancing CH4 and CO2 activation. The in-operando X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements confirmed that the Co catalyst was progressively oxidized from the surface to the bulk with reaction time, whereas CoNi and Ni remained relatively reduced during DRM. Density functional theory (DFT) calculation considering the high reaction temperature for DRM confirmed the unselective site arrangement between Co and Ni atoms in both the surface and bulk of the alloy nanoparticle (NP). The calculated heat of oxygen chemisorption became more exothermic in the order of Ni, CoNi, Co, consistent with the catalytic behavior. The comprehensive experimental and theoretical evidence provided herein clearly suggests improvement to the catalyst design protocol by selecting the appropriate composition of Co-Ni alloy.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
AlSabban B, Falivene L, Kozlov SM, Aguilar-Tapia A, Ould-Chikh S, et al. (2017) In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction. Applied Catalysis B: Environmental. Available: http://dx.doi.org/10.1016/j.apcatb.2017.04.076.
Publisher:
Elsevier BV
Journal:
Applied Catalysis B: Environmental
Issue Date:
2-May-2017
DOI:
10.1016/j.apcatb.2017.04.076
Type:
Article
ISSN:
0926-3373
Sponsors:
This work was funded by Saudi Arabia Basic Industries Corporation (SABIC) through a collaborative research project with King Abdullah University of Science and Technology (KAUST). The authors gratefully thank Dr. Lawrence D’Souza (SABIC) for technical advice and valuable contributions. Moreover, the authors acknowledge Mr. Dong-Chang Kang, KAUST Catalysis Center, and Dr. Manuel A. Roldan-Gutierrez, KAUST Core Laboratories, for their assistance with the DRIFTS and TEM measurements, respectively. We are also grateful for the computational resources for the XAS spectra acquired from the KAUST Supercomputing Laboratory using the supercomputer Shaheen II under project k1016.
Additional Links:
http://www.sciencedirect.com/science/article/pii/S0926337317303909
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorAl-Sabban, Bedouren
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorKozlov, Sergey M.en
dc.contributor.authorAguilar Tapia, Antonioen
dc.contributor.authorOuld-Chikh, Samyen
dc.contributor.authorHazemann, Jean-Louisen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorBasset, Jean-Marieen
dc.contributor.authorTakanabe, Kazuhiroen
dc.date.accessioned2017-05-09T08:34:34Z-
dc.date.available2017-05-09T08:34:34Z-
dc.date.issued2017-05-02en
dc.identifier.citationAlSabban B, Falivene L, Kozlov SM, Aguilar-Tapia A, Ould-Chikh S, et al. (2017) In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction. Applied Catalysis B: Environmental. Available: http://dx.doi.org/10.1016/j.apcatb.2017.04.076.en
dc.identifier.issn0926-3373en
dc.identifier.doi10.1016/j.apcatb.2017.04.076en
dc.identifier.urihttp://hdl.handle.net/10754/623410-
dc.description.abstractDry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals Co and Ni, which have high affinity with CO2 and high activity for CH4 decomposition, respectively. This study was focused on providing evidence of the capturing surface coverage of the reactive intermediates and the associated structural changes of the metals during DRM at high temperature using in-operando X-ray absorption spectroscopy (XAS). On the Co catalysts, the first-order effects with respect to CH4 pressure and negative-order effects with respect to CO2 pressure on the DRM rate are consistent with the competitive adsorption of the surface oxygen species on the same sites as the CH4 decomposition reaction. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst exhibits reactivity towards the DRM but with kinetic orders resembling Co catalyst, producing negligible carbon deposition by balancing CH4 and CO2 activation. The in-operando X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements confirmed that the Co catalyst was progressively oxidized from the surface to the bulk with reaction time, whereas CoNi and Ni remained relatively reduced during DRM. Density functional theory (DFT) calculation considering the high reaction temperature for DRM confirmed the unselective site arrangement between Co and Ni atoms in both the surface and bulk of the alloy nanoparticle (NP). The calculated heat of oxygen chemisorption became more exothermic in the order of Ni, CoNi, Co, consistent with the catalytic behavior. The comprehensive experimental and theoretical evidence provided herein clearly suggests improvement to the catalyst design protocol by selecting the appropriate composition of Co-Ni alloy.en
dc.description.sponsorshipThis work was funded by Saudi Arabia Basic Industries Corporation (SABIC) through a collaborative research project with King Abdullah University of Science and Technology (KAUST). The authors gratefully thank Dr. Lawrence D’Souza (SABIC) for technical advice and valuable contributions. Moreover, the authors acknowledge Mr. Dong-Chang Kang, KAUST Catalysis Center, and Dr. Manuel A. Roldan-Gutierrez, KAUST Core Laboratories, for their assistance with the DRIFTS and TEM measurements, respectively. We are also grateful for the computational resources for the XAS spectra acquired from the KAUST Supercomputing Laboratory using the supercomputer Shaheen II under project k1016.en
dc.publisherElsevier BVen
dc.relation.urlhttp://www.sciencedirect.com/science/article/pii/S0926337317303909en
dc.rightsUnder a Creative Commons licenseen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectDry Reforming of Methaneen
dc.subjectNickelen
dc.subjectCobalten
dc.subjectBimetalen
dc.subjectCarbon Depositionen
dc.subjectKineticsen
dc.subjectDensity Functional Theoryen
dc.subjectIn-operando X-ray Absorption Spectroscopyen
dc.titleIn-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reactionen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalApplied Catalysis B: Environmentalen
dc.eprint.versionPost-printen
dc.contributor.institutionInstitut Néel, UPR 2940 CNRS, 38042 Grenoble Cedex 9, Franceen
kaust.authorAl-Sabban, Bedouren
kaust.authorFalivene, Lauraen
kaust.authorKozlov, Sergey M.en
kaust.authorAguilar Tapia, Antonioen
kaust.authorOuld-Chikh, Samyen
kaust.authorCavallo, Luigien
kaust.authorBasset, Jean-Marieen
kaust.authorTakanabe, Kazuhiroen
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