A comparative study on cubic and tetragonal Ce-ZrO2 supported Rh catalysts for N2O decomposition

Youn, Jae-Rang; Ding, Honghe; Xia, Yujian; Moncada Vivas, Jorge; Colina-Ruiz, Roberto; Guo, Jinghua; Kim, Min-Jae

doi:10.1016/j.apsusc.2026.166042

A comparative study on cubic and tetragonal Ce-ZrO₂ supported Rh catalysts for N₂O decomposition

Journal Article · Wed Jan 21 00:00:00 EST 2026 · Applied Surface Science

DOI:https://doi.org/10.1016/j.apsusc.2026.166042· OSTI ID:3020268

Youn, Jae-Rang ^[1]; Ding, Honghe ^[2]; Xia, Yujian ^[3]; ^[4]; ^[5]; Guo, Jinghua ^[2]; ^[6]

Korea Institute of Energy Research (KIER), Daejeon (Korea, Republic of)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Univ. of California, Santa Cruz, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)
Korea Institute of Energy Research (KIER), Daejeon (Korea, Republic of); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Zirconium oxide (ZrO₂) exhibits strong synergy with cerium oxide (CeO₂), acting as a structural and electronic promoter during catalytic redox reactions. As a result, Ce-ZrO₂ composite oxides are widely used as supports in various catalytic systems. In our previous work, we demonstrated that the incorporation of Zr⁴⁺ into the CeO₂ lattice significantly enhanced Rh dispersion, improved redox ability, and stabilized surface Rh species, which collectively boosted the de-N₂O activity of Rh/Ce-ZrO₂ catalysts. Building on these findings, the present study emphasizes that the crystallographic phase of Ce-ZrO₂, governed by the Ce/Zr ratio, plays a decisive role in tuning the physicochemical environment of Rh active sites and thereby optimizing catalytic performance. In conclusion, tailoring the Ce/Zr ratio to favor the cubic fluorite structure emerges as a promising strategy for the rational design of highly active and stable catalysts for N₂O decomposition and potentially other redox-sensitive environmental applications.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0012704

Other Award/Contract Number:: 2438130

OSTI ID:: 3020268

Report Number(s):: BNL--229429-2026-JAAM

Journal Information:: Applied Surface Science, Journal Name: Applied Surface Science Vol. 727; ISSN 0169-4332

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (27)

Electronic‐Structure Interpretation: How Much Do We Understand Ce L₃ XANES? Kvashnina, Kristina O. Chemistry – A European Journal, Vol. 30, Issue 46 https://doi.org/10.1002/chem.202400755	journal	August 2024
Synthesis and luminescent properties of ZrO2 and Dy3+-activated ZrO2 powders Khajuria, Pooja; Mahajan, Rubby; Prakash, Ram Journal of Materials Science: Materials in Electronics, Vol. 32, Issue 23 https://doi.org/10.1007/s10854-021-07120-w	journal	October 2021
Heterogeneous catalytic decomposition of nitrous oxide Kapteijn, Freek; Rodriguez-Mirasol, José; Moulijn, Jacob A. Applied Catalysis B: Environmental, Vol. 9, Issue 1-4 https://doi.org/10.1016/0926-3373(96)90072-7	journal	September 1996
Formation and control of N2O in nitric acid production Pérez-Ramı́rez, J.; Kapteijn, F.; Schöffel, K. Applied Catalysis B: Environmental, Vol. 44, Issue 2 https://doi.org/10.1016/S0926-3373(03)00026-2	journal	August 2003
In-situ DRIFTS study of CeO2 supported Rh catalysts for N2O decomposition Zhu, Haiyang; Li, Yuejin; Zheng, Xiaolai Applied Catalysis A: General, Vol. 571 https://doi.org/10.1016/j.apcata.2018.12.020	journal	February 2019
On the importance of the catalyst redox properties in the N2O decomposition over alumina and ceria supported Rh, Pd and Pt Parres-Esclapez, S.; Illán-Gómez, M. J.; de Lecea, C. Salinas-Martínez Applied Catalysis B: Environmental, Vol. 96, Issue 3-4 https://doi.org/10.1016/j.apcatb.2010.02.034	journal	June 2010
Promotion of N2O decomposition by Zr4+-doped CeO2 used as support of Rh catalyst Kim, Min-Jae; Kim, Hye Jeong; Lee, Seung-Jae Catalysis Communications, Vol. 130 https://doi.org/10.1016/j.catcom.2019.105764	journal	October 2019
Preparation of a CeO2–ZrO2 based nano-composite with enhanced thermal stability by a novel chelating precipitation method Wang, Qi; Du, Fu; Hou, Yongke Ceramics International, Vol. 47, Issue 23 https://doi.org/10.1016/j.ceramint.2021.08.206	journal	December 2021
Enhanced catalytic activity of the Rh/γ-Al2O3 pellet catalyst for N2O decomposition using high Rh dispersion induced by citric acid Kim, Min-Jae; Kim, Young-Ji; Lee, Seung-Jae Chemical Engineering Research and Design, Vol. 141 https://doi.org/10.1016/j.cherd.2018.11.016	journal	January 2019
Effect of phase composition on X-ray absorption spectra of ZrO2 thin films Kikas, A.; Aarik, J.; Kisand, V. Journal of Electron Spectroscopy and Related Phenomena, Vol. 156-158 https://doi.org/10.1016/j.elspec.2006.11.031	journal	May 2007
Effect of surface properties controlled by Ce addition on CO2 methanation over Ni/Ce/Al2O3 catalyst Kim, Min-Jae; Youn, Jae-Rang; Kim, Hye Jeong International Journal of Hydrogen Energy, Vol. 45, Issue 46 https://doi.org/10.1016/j.ijhydene.2020.06.144	journal	September 2020
Study by isotopic gases and in situ spectroscopies (DRIFTS, XPS and Raman) of the N2O decomposition mechanism on Rh/CeO2 and Rh/γ-Al2O3 catalysts Parres-Esclapez, S.; Such-Basañez, I.; Illán-Gómez, M. J. Journal of Catalysis, Vol. 276, Issue 2 https://doi.org/10.1016/j.jcat.2010.10.001	journal	December 2010
Enhancing HT-WGS catalyst performance with stable monovalent copper species via electron supply from defect-induced MgO Kim, Min-Jae; Jeon, I-Jeong; Kim, Yong Jun Journal of Environmental Chemical Engineering, Vol. 13, Issue 1 https://doi.org/10.1016/j.jece.2024.115138	journal	February 2025
Facile control of surface properties in CeO2-promoted Mn/TiO2 catalyst for low-temperature selective catalytic reduction of NO by NH3 Kim, Min-Jae; Youn, Jae-Rang; Lee, Seung-Jae Journal of Industrial and Engineering Chemistry, Vol. 108 https://doi.org/10.1016/j.jiec.2022.01.023	journal	April 2022
Fabrication of carbon nanotube with high purity and crystallinity by methane decomposition over ceria-supported catalysts Kim, Min-Jae; Joo Park, Seon; Duk Kim, Ki Journal of Industrial and Engineering Chemistry, Vol. 119 https://doi.org/10.1016/j.jiec.2022.11.050	journal	March 2023
Regulating local coordination environment of rhodium single atoms in Rh/CeO2 catalysts for N2O decomposition Xie, Shaohua; Kim, Daekun; Ye, Kailong Journal of Rare Earths, Vol. 41, Issue 6 https://doi.org/10.1016/j.jre.2023.01.006	journal	June 2023
Fundamentals and Catalytic Applications of CeO ₂ -Based Materials Montini, Tiziano; Melchionna, Michele; Monai, Matteo Chemical Reviews, Vol. 116, Issue 10 https://doi.org/10.1021/acs.chemrev.5b00603	journal	April 2016
Oxygen K-edge X-ray Absorption Spectra Frati, Federica; Hunault, Myrtille O. J. Y.; de Groot, Frank M. F. Chemical Reviews, Vol. 120, Issue 9 https://doi.org/10.1021/acs.chemrev.9b00439	journal	April 2020
Oxygen K-Edge X-ray Absorption Spectra of ThO₂and CeO₂: Experiment, Interpretation, and Structural Effects Amidani, Lucia; Dumas, Thomas; Shuh, David K. The Journal of Physical Chemistry C, Vol. 127, Issue 6 https://doi.org/10.1021/acs.jpcc.2c07771	journal	February 2023
Cerium L _III -Edge XAS Investigation of the Structure of Crystalline and Amorphous Cerium Oxides Shahin, Ahmed M.; Grandjean, Fernande; Long, Gary J. Chemistry of Materials, Vol. 17, Issue 2 https://doi.org/10.1021/cm0492437	journal	January 2005
Methods for Preparation of Catalytic Materials Schwarz, James A.; Contescu, Cristian.; Contescu, Adriana. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a002	journal	May 1995
Mechanistic Studies of the Water–Gas Shift Reaction over Pt/Ce _x Zr _{1– x} O ₂ Catalysts: The Effect of Pt Particle Size and Zr Dopant Kalamaras, C. M.; Dionysiou, D. D.; Efstathiou, A. M. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs3006204	journal	November 2012
Unraveling the low-temperature activity of Rh–CeO₂ catalysts in CO oxidation: probing the local structure and Red-Ox transformation of Rh³⁺ species Fedorova, Elizaveta A.; Kardash, Tatyana Yu.; Kibis, Lidiya S. Physical Chemistry Chemical Physics, Vol. 25, Issue 4 https://doi.org/10.1039/D2CP04503F	journal	January 2023
Understanding the role of supported Rh atoms and clusters during hydroformylation and CO hydrogenation reactions with in situ/operando XAS and DRIFT spectroscopy Sarma, Bidyut Bikash; Neukum, Dominik; Doronkin, Dmitry E. Chemical Science, Vol. 15, Issue 31 https://doi.org/10.1039/D4SC02907K	journal	January 2024
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
The Inner Shell Spectroscopy beamline at NSLS-II: a facility for in situ and operando X-ray absorption spectroscopy for materials research Leshchev, Denis; Rakitin, Maksim; Luvizotto, Bruno Journal of Synchrotron Radiation, Vol. 29, Issue 4 https://doi.org/10.1107/S160057752200460X	journal	May 2022
Effect of RhOx/CeO2 Calcination on Metal-Support Interaction and Catalytic Activity for N2O Decomposition Rico-Pérez, Verónica; Bueno-López, Agustin Applied Sciences, Vol. 4, Issue 3 https://doi.org/10.3390/app4030468	journal	September 2014

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