The Triple Component Interface of Ni–Co–Ce: Growth, Chemical State, and Stability of NiCo Bimetallic Particles on Reducible CeO2(111) Thin Films

Paudyal, Nishan; Ara, Tasnim; Du Hill, Linze; Senanayake, Sanjaya D.; Zhou, Jing

doi:10.1021/acs.jpcc.4c04802

Title: The Triple Component Interface of Ni–Co–Ce: Growth, Chemical State, and Stability of NiCo Bimetallic Particles on Reducible CeO₂(111) Thin Films

Journal Article · 24 September 2024 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.4c04802 · OSTI ID:2481976

^[1]; Ara, Tasnim ^[1]; Du Hill, Linze ^[1];

^[2];

^[1]

Univ. of Wyoming, Laramie, WY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

The growth of NiCo particles at low coverages over reducible CeO₂(111) thin films producing a triple interface between Ni-Co-Ce was investigated by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), which was compared to that of monometallic Ni and Co particles. XPS data show that deposition of either Ni or Co on CeO₂ at 300 K causes a partial reduction of Ce⁴⁺ cations to Ce³⁺ ions. At 0.3 monolayer (ML), XPS detects Co²⁺ on CeO₂. However, both Ni⁰ and Ni²⁺ are present as major species at 300 K and annealing causes a significant increase of Ni²⁺ in Ni particles. Deposition of 0.3 ML Co over 0.3 ML Ni on CeO₂ at 300 K induces reduction of Ni²⁺ to metallic Ni and Ni⁰ was found as predominant species. Unlike for Co/CeO₂, metallic Co was also present over the Co-Ni/CeO₂ surface in addition to Co²⁺. Further, this behavior indicates the formation of NiCo bimetallic particles with the possibility of Co diffusion to the interface of Ni/ceria. With heating, the intermixing of Ni and Co atoms in bimetallic particles on CeO₂ was facilitated. Furthermore, oxidation of both metals and ceria occurred as a result of the diffusion of lattice oxygen from the bulk of ceria to the surface. A slight increase in Ni²⁺ was observed after heating Co-Ni/CeO₂ to 500 K or higher. Co became Co²⁺ with heating to 800 K. Our STM results confirm the formation of NiCo bimetallic particles on CeO₂ at 300 K and further suggest that the addition of Co can help inhibit the sintering of Ni particles at higher temperatures. Bimetallic particles were also obtained by depositing Ni over existing Co particles on CeO₂. However, our XPS data demonstrate that the deposition order of Co and Ni plays a role in the chemical state of these two metals in bimetallic particles, likely attributed to the difference in their compositions at the bimetallic particle surface as well as the metal-support interface.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2481976

Report Number(s):: BNL-226368-2024-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 39 Vol. 128; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

High Activity of Ce1−xNixO2−y for H2 Production through Ethanol Steam Reforming: Tuning Catalytic Performance through Metal-Oxide Interactions Zhou, Gong; Barrio, Laura; Agnoli, Stefano Angewandte Chemie, Vol. 122, Issue 50 https://doi.org/10.1002/ange.201004966	journal	November 2010
Dry Reforming of Methane on a Highly-Active Ni-CeO ₂ Catalyst: Effects of Metal-Support Interactions on C−H Bond Breaking Liu, Zongyuan; Grinter, David C.; Lustemberg, Pablo G. Angewandte Chemie International Edition, Vol. 55, Issue 26 https://doi.org/10.1002/anie.201602489	journal	May 2016
In Situ Investigation of Methane Dry Reforming on Metal/Ceria(111) Surfaces: Metal-Support Interactions and C−H Bond Activation at Low Temperature Liu, Zongyuan; Lustemberg, Pablo; Gutiérrez, Ramón A. Angewandte Chemie International Edition, Vol. 56, Issue 42 https://doi.org/10.1002/anie.201707538	journal	September 2017
Surface State and Catalytic Performance of Ceria-Supported Cobalt Catalysts in the Steam Reforming of Ethanol Turczyniak, Sylwia; Greluk, Magdalena; Słowik, Grzegorz ChemCatChem, Vol. 9, Issue 5 https://doi.org/10.1002/cctc.201601343	journal	February 2017
Water–Gas Shift and CO Methanation Reactions over Ni–CeO2(111) Catalysts Senanayake, Sanjaya D.; Evans, Jaime; Agnoli, Stefano Topics in Catalysis, Vol. 54, Issue 1-4 https://doi.org/10.1007/s11244-011-9645-6	journal	January 2011
Growth and Structure of Ni–Au Bimetallic Particles on Reducible CeO2(111) Zhou, Yinghui; Peterson, Erik Wayne; Zhou, Jing Topics in Catalysis, Vol. 58, Issue 2-3 https://doi.org/10.1007/s11244-014-0352-y	journal	December 2014
Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces Mullins, D. R.; Overbury, S. H.; Huntley, D. R. Surface Science, Vol. 409, Issue 2 https://doi.org/10.1016/S0039-6028(98)00257-X	journal	July 1998
Ordered cerium oxide thin films grown on Ru(0001) and Ni(111) Mullins, D.R.; Radulovic, P.V.; Overbury, S.H. Surface Science, Vol. 429, Issue 1-3, p. 186-198 https://doi.org/10.1016/S0039-6028(99)00369-6	journal	June 1999
Nanoscale architecture of ceria-based model catalysts: Pt–Co nanostructures on well-ordered CeO2(111) thin films Lykhach, Yaroslava; Skála, Tomáš; Neitzel, Armin Chinese Journal of Catalysis, Vol. 41, Issue 6 https://doi.org/10.1016/S1872-2067(19)63462-5	journal	June 2020
Water-gas shift: comparative screening of metal promoters for metal/ceria systems and role of the metal Jacobs, G. Applied Catalysis A: General, Vol. 258, Issue 2 https://doi.org/10.1016/j.apcata.2003.09.007	journal	February 2004
Dry reforming of methane over nickel catalysts supported on magnesium aluminate spinels Guo, Jianjun; Lou, Hui; Zhao, Hong Applied Catalysis A: General, Vol. 273, Issue 1-2 https://doi.org/10.1016/j.apcata.2004.06.014	journal	October 2004
Enhanced dry reforming of methane on Ni and Ni-Pt catalysts synthesized by atomic layer deposition Gould, Troy D.; Montemore, Matthew M.; Lubers, Alia M. Applied Catalysis A: General, Vol. 492 https://doi.org/10.1016/j.apcata.2014.11.037	journal	February 2015
Dry reforming of methane over CeO2 supported Ni, Co and Ni–Co catalysts Ay, Hale; Üner, Deniz Applied Catalysis B: Environmental, Vol. 179 https://doi.org/10.1016/j.apcatb.2015.05.013	journal	December 2015
Effects of oxide supports on the CO2 reforming of ethane over Pt-Ni bimetallic catalysts Xie, Zhenhua; Yan, Binhang; Lee, Ji Hoon Applied Catalysis B: Environmental, Vol. 245 https://doi.org/10.1016/j.apcatb.2018.12.070	journal	May 2019
Highly active Ni/CeO2 catalyst for CO2 methanation: Preparation and characterization Rui, Ning; Zhang, Xiaoshan; Zhang, Feng Applied Catalysis B: Environmental, Vol. 282 https://doi.org/10.1016/j.apcatb.2020.119581	journal	March 2021
Morphology and electronic properties of Ni supported on Mn-doped CeO2(1 1 1) thin films Ginting, Elfrida; Du, Linze; Zhou, Jing Applied Surface Science, Vol. 514 https://doi.org/10.1016/j.apsusc.2020.145850	journal	June 2020
Dry reforming of methane over Pt-Ni/CeO2 catalysts: Effect of the metal composition on the stability Araiza, Daniel G.; Arcos, Diana G.; Gómez-Cortés, Antonio Catalysis Today, Vol. 360 https://doi.org/10.1016/j.cattod.2019.06.018	journal	January 2021
Elucidating the impact of Ni and Co loading on the selectivity of bimetallic NiCo catalysts for dry reforming of methane Horlyck, Jonathan; Lawrey, Catherine; Lovell, Emma C. Chemical Engineering Journal, Vol. 352 https://doi.org/10.1016/j.cej.2018.07.009	journal	November 2018
Bimetallic Nickel-Cobalt catalysts and their application in dry reforming reaction of methane Guo, Shuowen; Sun, Yinghui; Zhang, Yanbin Fuel, Vol. 358 https://doi.org/10.1016/j.fuel.2023.130290	journal	February 2024
CO2 hydrogenation on Co/CeO2-δ catalyst: Morphology effect from CeO2 support Xie, Fengqiong; Xu, Shiyu; Deng, Lidan International Journal of Hydrogen Energy, Vol. 45, Issue 51 https://doi.org/10.1016/j.ijhydene.2020.05.260	journal	October 2020
Metal–support interactions and reactivity of Co/CeO2 catalysts in the Fischer–Tropsch synthesis reaction Spadaro, L.; Arena, F.; Granados, M. Journal of Catalysis, Vol. 234, Issue 2 https://doi.org/10.1016/j.jcat.2005.07.006	journal	September 2005
Mesoporous Co3O4–CeO2 and Pd/Co3O4–CeO2 catalysts: Synthesis, characterization and mechanistic study of their catalytic properties for low-temperature CO oxidation Luo, J.; Meng, M.; Li, X. Journal of Catalysis, Vol. 254, Issue 2 https://doi.org/10.1016/j.jcat.2008.01.007	journal	March 2008
Morphology changes induced by strong metal–support interaction on a Ni–ceria catalytic system Gonzalezdelacruz, V.; Holgado, J.; Pereniguez, R. Journal of Catalysis, Vol. 257, Issue 2 https://doi.org/10.1016/j.jcat.2008.05.009	journal	July 2008
Study of catalyst deactivation and reaction mechanism of steam reforming, partial oxidation, and oxidative steam reforming of ethanol over Co/CeO2 catalyst de Lima, Sania M.; da Silva, Adriana M.; da Costa, Lídia O. O. Journal of Catalysis, Vol. 268, Issue 2 https://doi.org/10.1016/j.jcat.2009.09.025	journal	December 2009
Near ambient pressure XPS investigation of the interaction of ethanol with Co/CeO2(111) Óvári, L.; Krick Calderon, S.; Lykhach, Y. Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.07.015	journal	November 2013
CO2 reforming of methane over Ni-Ru supported catalysts: On the nature of active sites by operando DRIFTS study M., A. Álvarez; Bobadilla, L. F.; Garcilaso, V. Journal of CO2 Utilization, Vol. 24 https://doi.org/10.1016/j.jcou.2018.01.027	journal	March 2018
CeO2-supported Fe, Co and Ni toward CO2 hydrogenation: Tuning catalytic performance via metal-support interaction Li, Bolang; Wang, Fei; Li, Kai Journal of Rare Earths, Vol. 41, Issue 6 https://doi.org/10.1016/j.jre.2023.02.009	journal	June 2023
Oxidation states of active catalytic centers in ethanol steam reforming reaction on ceria based Rh promoted Co catalysts: An XPS study Varga, Erika; Ferencz, Zsuzsa; Oszkó, Albert Journal of Molecular Catalysis A: Chemical, Vol. 397 https://doi.org/10.1016/j.molcata.2014.11.010	journal	February 2015
The surface chemistry of cerium oxide Mullins, David R. Surface Science Reports, Vol. 70, Issue 1 https://doi.org/10.1016/j.surfrep.2014.12.001	journal	March 2015
Growth and alloy formation of ultrathin Ni films on Co/Pt(111) Ho, H. Y.; Chen, Y. J.; Shern, C. S. Surface Science, Vol. 600, Issue 5 https://doi.org/10.1016/j.susc.2005.12.037	journal	March 2006
Morphology and defect structure of the CeO2(111) films grown on Ru(0001) as studied by scanning tunneling microscopy Lu, J. -L.; Gao, H. -J.; Shaikhutdinov, S. Surface Science, Vol. 600, Issue 22 https://doi.org/10.1016/j.susc.2006.08.023	journal	November 2006
Alloy formation of Co/Ni/Pt(111) Ho, H. Y.; Lin, Y. S.; Huang, E. J. Surface Science, Vol. 601, Issue 3 https://doi.org/10.1016/j.susc.2006.10.028	journal	February 2007
A STM study of Ni-Rh bimetallic particles on reducible CeO2(111) Zhou, Yinghui; Du, Linze; Zou, Yunkai Surface Science, Vol. 681 https://doi.org/10.1016/j.susc.2018.10.013	journal	March 2019
Morphology and chemical states of Ni supported on Ti-modified CeOx(111) interfaces Du, Linze; Ginting, Elfrida; Zhou, Jing Surface Science, Vol. 699 https://doi.org/10.1016/j.susc.2020.121624	journal	September 2020
Oxidation of Sn at the Cluster–Support Interface: Sn and Pt–Sn Clusters on TiO₂(110) Beniwal, Sumit; Chai, Wenrui; Metavarayuth, Kamolrat The Journal of Physical Chemistry C, Vol. 125, Issue 32 https://doi.org/10.1021/acs.jpcc.1c03338	journal	August 2021
The Structure, Oxidation States, and Energetics of Co Nanoparticles on CeO₂(111): An STM and DFT Study Rahman, Md. Saeedur; Paudyal, Nishan; Hill, Linze Du The Journal of Physical Chemistry C, Vol. 128, Issue 43 https://doi.org/10.1021/acs.jpcc.4c03911	journal	August 2024
The Interaction of Cobalt with CeO ₂ (111) Prepared on Cu(111) Vári, Gábor; Óvári, László; Papp, Christian The Journal of Physical Chemistry C, Vol. 119, Issue 17 https://doi.org/10.1021/acs.jpcc.5b00626	journal	April 2015
Low-Temperature Dissociation of CO ₂ on a Ni/CeO ₂ (111)/Ru(0001) Model Catalyst Kong, Dandan; Zhu, Junfa; Ernst, Karl-Heinz The Journal of Physical Chemistry C, Vol. 120, Issue 11 https://doi.org/10.1021/acs.jpcc.5b10338	journal	March 2016
Ni Nanoparticles on CeO ₂ (111): Energetics, Electron Transfer, and Structure by Ni Adsorption Calorimetry, Spectroscopies, and Density Functional Theory Mao, Zhongtian; Lustemberg, Pablo G.; Rumptz, John R. ACS Catalysis, Vol. 10, Issue 9 https://doi.org/10.1021/acscatal.0c00333	journal	April 2020
Nature of the Active Sites on Ni/CeO ₂ Catalysts for Methane Conversions Lustemberg, Pablo G.; Mao, Zhongtian; Salcedo, Agustín ACS Catalysis, Vol. 11, Issue 16 https://doi.org/10.1021/acscatal.1c02154	journal	August 2021
Room-Temperature Activation of Methane and Dry Re-forming with CO ₂ on Ni-CeO ₂ (111) Surfaces: Effect of Ce ³⁺ Sites and Metal–Support Interactions on C–H Bond Cleavage Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b02360	journal	November 2016
In Situ Elucidation of the Active State of Co–CeO _x Catalysts in the Dry Reforming of Methane: The Important Role of the Reducible Oxide Support and Interactions with Cobalt Zhang, Feng; Liu, Zongyuan; Zhang, Shuhao ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b03640	journal	March 2018
Effect of Support Particle Size in Steam Reforming of Ethanol over Co/CeO ₂ Catalysts Soykal, I. Ilgaz; Sohn, Hyuntae; Ozkan, Umit S. ACS Catalysis, Vol. 2, Issue 11 https://doi.org/10.1021/cs3004159	journal	September 2012
Growth of Pt Nanoparticles on Reducible CeO ₂ (111) Thin Films: Effect of Nanostructures and Redox Properties of Ceria Zhou, Yinghui; Perket, Justin M.; Zhou, Jing The Journal of Physical Chemistry C, Vol. 114, Issue 27 https://doi.org/10.1021/jp1007279	journal	June 2010
Unusual Physical and Chemical Properties of Ni in Ce _{1− x} Ni _x O _{2− y} Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction Barrio, Laura; Kubacka, Ania; Zhou, Gong The Journal of Physical Chemistry C, Vol. 114, Issue 29 https://doi.org/10.1021/jp103958u	journal	June 2010
In Situ XAS Study of Synergic Effects on Ni–Co/ZrO ₂ Methane Reforming Catalysts Gonzalez-delaCruz, Victor M.; Pereñiguez, Rosa; Ternero, Fatima The Journal of Physical Chemistry C, Vol. 116, Issue 4 https://doi.org/10.1021/jp2092048	journal	January 2012
Interactions of Ni Nanoparticles with Reducible CeO ₂ (111) Thin Films Zhou, Yinghui; Zhou, Jing The Journal of Physical Chemistry C, Vol. 116, Issue 17 https://doi.org/10.1021/jp300259y	journal	April 2012
Understanding the Nucleation and Growth of Metals on TiO ₂ : Co Compared to Au, Ni, and Pt Galhenage, Randima P.; Yan, Hui; Tenney, Samuel A. The Journal of Physical Chemistry C, Vol. 117, Issue 14 https://doi.org/10.1021/jp401283k	journal	March 2013
Interaction of Gold with Cerium Oxide Supports: CeO ₂ (111) Thin Films vs CeO _x Nanoparticles Baron, M.; Bondarchuk, O.; Stacchiola, D. The Journal of Physical Chemistry C, Vol. 113, Issue 15 https://doi.org/10.1021/jp9001753	journal	March 2009
Effect of Ceria Support on the Structure of Ni Nanoparticles Zhou, Yinghui; Perket, Justin M.; Crooks, Adam B. The Journal of Physical Chemistry Letters, Vol. 1, Issue 9 https://doi.org/10.1021/jz1003044	journal	April 2010
Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles Vayssilov, Georgi N.; Lykhach, Yaroslava; Migani, Annapaola Nature Materials, Vol. 10, Issue 4 https://doi.org/10.1038/nmat2976	journal	March 2011
Experimental and computational investigation on underlying factors promoting high coke resistance in NiCo bimetallic catalysts during dry reforming of methane Saelee, Tinnakorn; Lerdpongsiripaisarn, Mongkol; Rittiruam, Meena Scientific Reports, Vol. 11, Issue 1 https://doi.org/10.1038/s41598-020-80287-0	journal	January 2021
In situ spectroscopic detection ofSMSI effect in a Ni/CeO ₂ system: hydrogen-induced burial and dig out of metallic nickel Caballero, Alfonso; Holgado, Juan P.; Gonzalez-delaCruz, Victor M. Chem. Commun., Vol. 46, Issue 7 https://doi.org/10.1039/B920803H	journal	January 2010
Peculiar surface–interface properties of nanocrystalline ceria–cobalt oxides with enhanced oxygen storage capacity Qiu, Nan; Zhang, Jing; Wu, Ziyu Phys. Chem. Chem. Phys., Vol. 16, Issue 41 https://doi.org/10.1039/C4CP03390F	journal	January 2014
Steering the formation of supported Pt–Sn nanoalloys by reactive metal–oxide interaction Neitzel, Armin; Kovács, Gábor; Lykhach, Yaroslava RSC Advances, Vol. 6, Issue 89 https://doi.org/10.1039/C6RA18801J	journal	January 2016
Ni/Co in and on CeO₂: a comparative study on the dry reforming reaction Yadav, Pradeep Kumar; Patrikar, Kalyani; Mondal, Anirban Sustainable Energy & Fuels, Vol. 7, Issue 16 https://doi.org/10.1039/D3SE00649B	journal	January 2023
The highly active catalysts of nanocomposite K–Co–CeO2 for soot combustion Liu, Jian; Zhao, Zhen; Xu, Junfeng Chemical Communications, Vol. 47, Issue 39 https://doi.org/10.1039/c1cc14338g	journal	January 2011
Satellite structure in the X-ray photoelectron spectra of some binary and mixed oxides of lanthanum and cerium Burroughs, Peter; Hamnett, Andrew; Orchard, Anthony F. Journal of the Chemical Society, Dalton Transactions, Issue 17 https://doi.org/10.1039/dt9760001686	journal	January 1976
Charge transfer and spillover phenomena in ceria-supported iridium catalysts: A model study Lykhach, Yaroslava; Kubát, Jan; Neitzel, Armin The Journal of Chemical Physics, Vol. 151, Issue 20 https://doi.org/10.1063/1.5126031	journal	November 2019
Growth, sintering, and chemical states of Co supported on reducible CeO₂(111) thin films: The effects of the metal coverage and the nature of the support Zhou, Jing; Du, Linze; Braedt, Daniel L. The Journal of Chemical Physics, Vol. 154, Issue 4 https://doi.org/10.1063/5.0036952	journal	January 2021
The Surface Free Energies of Solid Chemical Elements: Calculation from Internal Free Enthalpies of Atomization Mezey, L. Z.; Giber, J. Japanese Journal of Applied Physics, Vol. 21, Issue Part 1, No. 11 https://doi.org/10.1143/JJAP.21.1569	journal	November 1982
Surface Structural and Magnetic Properties of Cobalt Bilayer Deposited on Pt(111) with Ni Buffer Layer Ho, Huei-Ying; Shern, Ching-Song Japanese Journal of Applied Physics, Vol. 50, Issue 8R https://doi.org/10.7567/JJAP.50.083001	journal	August 2011

Similar Records

Infrared reflection absorption spectroscopy and temperature-programmed desorption studies of CO adsorption on Ni/CeO₂(111) thin films: The role of the ceria support

Journal Article · 2021 · Journal of Vacuum Science and Technology A · OSTI ID:1839209

Peterson, Erik W.; Wang, Huanru; Liu, Zongyuan; +4 more

Growth, sintering, and chemical states of Co supported on reducible CeO₂(111) thin films: The effects of the metal coverage and the nature of the support

Journal Article · 2021 · Journal of Chemical Physics · OSTI ID:1777437

Zhou, Jing; Du, Linze; Braedt, Daniel L.; +2 more

Ni Nanoparticles on CeO₂(111): Energetics, Electron Transfer, and Structure by Ni Adsorption Calorimetry, Spectroscopies, and Density Functional Theory

Journal Article · 2020 · ACS Catalysis · OSTI ID:1774931

Mao, Zhongtian; Lustemberg, Pablo G.; Rumptz, John R.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: The Triple Component Interface of Ni–Co–Ce: Growth, Chemical State, and Stability of NiCo Bimetallic Particles on Reducible CeO2(111) Thin Films

Citation Formats

References (62)

Similar Records

Related Subjects

Title: The Triple Component Interface of Ni–Co–Ce: Growth, Chemical State, and Stability of NiCo Bimetallic Particles on Reducible CeO₂(111) Thin Films