Does H 2 Temperature‐Programmed Reduction Always Probe Solid‐State Redox Chemistry? The Case of Pt/CeO 2

Lee, Jaeha; Christopher, Phillip

doi:10.1002/ange.202414388

Title: Does H ₂ Temperature‐Programmed Reduction Always Probe Solid‐State Redox Chemistry? The Case of Pt/CeO ₂

Journal Article · 05 November 2024 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202414388 · OSTI ID:2524091

^[1]; Christopher, Phillip ^[2]

Department of Chemical Engineering University of California, Santa Barbara Santa Barbara CA 93106-5080 United States, Department of Applied Chemistry Kyungpook National University Daegu 41566 Republic of Korea
Department of Chemical Engineering University of California, Santa Barbara Santa Barbara CA 93106-5080 United States

Abstract Redox reactions on the surface of transition metal oxides are of broad interest in thermo, photo, and electrocatalysis. H ₂ temperature‐programmed reduction (H ₂ ‐TPR) is commonly used to probe oxide reducibility by measuring the rate of H ₂ consumption during temperature ramps, assuming that this rate is controlled by oxide reduction. However, oxide reduction involves several elementary steps, such as H ₂ dissociation and H‐spillover, before surface reduction and H ₂ O formation occur. In this study, we evaluated the kinetics of H ₂ consumption over CeO ₂ and Pt/CeO ₂ with varying Pt loadings and structures to identify the elementary steps probed by H ₂ ‐TPR. Literature often attributes changes in H ₂ ‐TPR characteristics with Pt addition to increased CeO ₂ reducibility. However, our analysis revealed that the H ₂ consumption rate is measurement of the rate of H‐spillover at Pt‐CeO ₂ interfaces and is determined by the concentration of Pt species on Pt nanoclusters that dissociate H ₂ . Therefore, lower temperature H ₂ consumption observed with Pt addition does not indicate higher CeO ₂ reducibility. Measurements on samples with mixtures of Pt single‐atoms and nanoclusters demonstrated that H ₂ ‐TPR can effectively quantify dilute Pt nanocluster concentrations, suggesting caution in directly linking H ₂ ‐TPR characteristics to oxide reducibility while highlighting alternative material insights that can be gleaned.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021124

OSTI ID:: 2524091

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 2 Vol. 137; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (45)

Rationalization of Interactions in Precious Metal/Ceria Catalysts Using the d-Band Center Model Acerbi, N.; Tsang, S. C. Edman; Jones, G. Angewandte Chemie International Edition, Vol. 52, Issue 30 https://doi.org/10.1002/anie.201300130	journal	June 2013
Surface Density Dependent Catalytic Activity of Single Palladium Atoms Supported on Ceria** Kim, Yongseon; Collinge, Greg; Lee, Mal‐Soon Angewandte Chemie International Edition, Vol. 60, Issue 42 https://doi.org/10.1002/anie.202105750	journal	July 2021
Redox and Chemisorptive Properties of Ex-Chloride and Ex-Nitrate Rh/Ce0.6Zr0.4O2 Catalysts Fornasiero, Paolo; Hickey, Neal; Kašpar, Jan Journal of Catalysis, Vol. 189, Issue 2 https://doi.org/10.1006/jcat.1999.2713	journal	January 2000
Reduction and Oxygen Storage Behavior of Noble Metals Supported on Silica-Doped Ceria Rocchini, E. Journal of Catalysis, Vol. 211, Issue 2 https://doi.org/10.1016/S0021-9517(02)93719-X	journal	October 2002
The use of temperature-programmed and dynamic/transient methods in catalysis: characterization of ceria-based, model three-way catalysts Boaro, Marta; Vicario, Michela; de Leitenburg, Carla Catalysis Today, Vol. 77, Issue 4 https://doi.org/10.1016/S0920-5861(02)00383-8	journal	January 2003
Alleviating inhibitory effect of H2 on low-temperature water-gas shift reaction activity of Pt/CeO2 catalyst by forming CeO2 nano-patches on Pt nano-particles Lee, Jaeha; Shin, Dongjae; Lee, Eunwon Applied Catalysis B: Environmental, Vol. 305 https://doi.org/10.1016/j.apcatb.2021.121038	journal	May 2022
Toward gasoline vehicles with zero harmful emissions by storing NO at Pd nanoparticle–CeO2 interface during the cold-start period Lee, Jaeha; Kim, Yongwoo; Hwang, Sungha Chem Catalysis, Vol. 2, Issue 9 https://doi.org/10.1016/j.checat.2022.07.004	journal	September 2022
“Redox” vs “associative formate with –OH group regeneration” WGS reaction mechanism on Pt/CeO2: Effect of platinum particle size Kalamaras, Christos M.; Americanou, Sofia; Efstathiou, Angelos M. Journal of Catalysis, Vol. 279, Issue 2 https://doi.org/10.1016/j.jcat.2011.01.024	journal	April 2011
Hydrogen spillover monitored by resonant photoemission spectroscopy Lykhach, Yaroslava; Staudt, Thorsten; Vorokhta, Mykhailo Journal of Catalysis, Vol. 285, Issue 1 https://doi.org/10.1016/j.jcat.2011.09.002	journal	January 2012
Facet-dependent electronic state of Pt single atoms anchoring on CeO2 nanocrystal for CO (preferential) oxidation Chen, Yang; Wan, Qiang; Cao, Liru Journal of Catalysis, Vol. 415 https://doi.org/10.1016/j.jcat.2022.10.002	journal	November 2022
Role of CeO2 in promoting the spillover in CO oxidation reaction over platinum nanoparticle-supported CeO2 catalyst Lee, Eunwon; Lee, Jaeha; Hwang, Sungha Journal of Catalysis, Vol. 417 https://doi.org/10.1016/j.jcat.2022.12.030	journal	January 2023
Reaction Kinetics in Differential Thermal Analysis Kissinger, H. E. Analytical Chemistry, Vol. 29, Issue 11 https://doi.org/10.1021/ac60131a045	journal	November 1957
Relevance of IR Spectroscopy of Adsorbed CO for the Characterization of Heterogeneous Catalysts Containing Isolated Atoms Meunier, Frederic C. The Journal of Physical Chemistry C, Vol. 125, Issue 40 https://doi.org/10.1021/acs.jpcc.1c06784	journal	September 2021
Hydrogen Interaction with Oxide Supports in the Presence and Absence of Platinum Beck, Arik; Rzepka, Przemyslaw; Marshall, Kenneth P. The Journal of Physical Chemistry C, Vol. 126, Issue 41 https://doi.org/10.1021/acs.jpcc.2c05478	journal	October 2022
On the Utility of Ce³⁺ Spin−Orbit Transitions in the Interpretation of Rate Data in Ceria Catalysis: Theory, Validation, and Application Afrin, Sadia; Bollini, Praveen The Journal of Physical Chemistry C, Vol. 127, Issue 1 https://doi.org/10.1021/acs.jpcc.2c06637	journal	December 2022
Comprehensive Study of the Ceria–H₂ System: Effect of the Reaction Conditions on the Reduction Extent and Intermediates Schweke, D.; Shelly, L.; Ben David, R. The Journal of Physical Chemistry C, Vol. 124, Issue 11 https://doi.org/10.1021/acs.jpcc.9b11975	journal	February 2020
Theoretical Studies on the Stability and Reactivity of the Metal-Doped CeO₂(100) Surface: Toward H₂ Dissociation and Oxygen Vacancy Formation Zhang, Wei; Pu, Min; Lei, Ming Langmuir, Vol. 36, Issue 21 https://doi.org/10.1021/acs.langmuir.0c00644	journal	May 2020
Hydrogen Adsorption at the Au/TiO₂ Interface: Quantitative Determination and Spectroscopic Signature of the Reactive Interface Hydroxyl Groups at the Active Site Mahdavi-Shakib, Akbar; Rich, Lauren C.; Whittaker, Todd N. ACS Catalysis, Vol. 11, Issue 24 https://doi.org/10.1021/acscatal.1c04419	journal	December 2021
Role of Low-Coordinated Ce in Hydride Formation and Selective Hydrogenation Reactions on CeO₂ Surfaces Wang, Zhi-Qiang; Chu, De-Ren; Zhou, Hui ACS Catalysis, Vol. 12, Issue 1 https://doi.org/10.1021/acscatal.1c04856	journal	December 2021
Platinum Group Metal Catalyst (RuO_x, PtO_x, and IrO_x)-Decorated Ceria-Zirconia Solid Solution as High Active Oxygen Carriers for Solar Thermochemical CO₂ Splitting Chen, Zhenpan; Jiang, Qingqing; An, Hongyu ACS Catalysis, Vol. 12, Issue 13 https://doi.org/10.1021/acscatal.2c02044	journal	June 2022
Limits of Detection for EXAFS Characterization of Heterogeneous Single-Atom Catalysts Finzel, Jordan; Sanroman Gutierrez, Kenzie M.; Hoffman, Adam S. ACS Catalysis, Vol. 13, Issue 9 https://doi.org/10.1021/acscatal.3c01116	journal	April 2023
Water-Mediated Mars–Van Krevelen Mechanism for CO Oxidation on Ceria-Supported Single-Atom Pt ₁ Catalyst Wang, Chunlei; Gu, Xiang-Kui; Yan, Huan ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b02685	journal	December 2016
Design Strategies for Efficient Nonstoichiometric Mixed Metal Oxide Electrocatalysts: Correlating Measurable Oxide Properties to Electrocatalytic Performance Samira, Samji; Gu, Xiang-Kui; Nikolla, Eranda ACS Catalysis, Vol. 9, Issue 11 https://doi.org/10.1021/acscatal.9b02505	journal	September 2019
Relationship between Atomic Scale Structure and Reactivity of Pt Catalysts: Hydrodeoxygenation of m -Cresol over Isolated Pt Cations and Clusters Resasco, Joaquin; Yang, Feifei; Mou, Tong ACS Catalysis, Vol. 10, Issue 1 https://doi.org/10.1021/acscatal.9b04330	journal	November 2019
The Extent of Platinum-Induced Hydrogen Spillover on Cerium Dioxide Beck, Arik; Kazazis, Dimitrios; Ekinci, Yasin ACS Nano, Vol. 17, Issue 2 https://doi.org/10.1021/acsnano.2c08152	journal	December 2022
Breaking H₂ with CeO₂: Effect of Surface Termination Matz, Olivier; Calatayud, Monica ACS Omega, Vol. 3, Issue 11 https://doi.org/10.1021/acsomega.8b02410	journal	November 2018
Hydrogen Spillover. Facts and Fiction Prins, R. Chemical Reviews, Vol. 112, Issue 5 https://doi.org/10.1021/cr200346z	journal	February 2012
Shape-Dependent Activity of Ceria in Soot Combustion Aneggi, Eleonora; Wiater, Dawid; de Leitenburg, Carla ACS Catalysis, Vol. 4, Issue 1 https://doi.org/10.1021/cs400850r	journal	December 2013
Experimental and Theoretical Studies on the Reaction of H ₂ with NiO: Role of O Vacancies and Mechanism for Oxide Reduction Rodriguez, José A.; Hanson, Jonathan C.; Frenkel, Anatoly I. Journal of the American Chemical Society, Vol. 124, Issue 2 https://doi.org/10.1021/ja0121080	journal	January 2002
Reduction of CuO and Cu ₂ O with H ₂ : H Embedding and Kinetic Effects in the Formation of Suboxides Kim, Jae Y.; Rodriguez, José A.; Hanson, Jonathan C. Journal of the American Chemical Society, Vol. 125, Issue 35 https://doi.org/10.1021/ja0301673	journal	September 2003
Controllable Conversion of Platinum Nanoparticles to Single Atoms in Pt/CeO₂ by Laser Ablation for Efficient CO Oxidation Fu, Ninghua; Liang, Xiao; Wang, Xiaolu Journal of the American Chemical Society, Vol. 145, Issue 17 https://doi.org/10.1021/jacs.2c11739	journal	March 2023
Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO ₂ DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b07093	journal	September 2017
Toward an Understanding of Selective Alkyne Hydrogenation on Ceria: On the Impact of O Vacancies on H ₂ Interaction with CeO ₂ (111) Werner, Kristin; Weng, Xuefei; Calaza, Florencia Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b10021	journal	November 2017
Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO ₂ Resasco, Joaquin; DeRita, Leo; Dai, Sheng Journal of the American Chemical Society, Vol. 142, Issue 1 https://doi.org/10.1021/jacs.9b09156	journal	December 2019
Pt-Mediated Reversible Reduction and Expansion of CeO ₂ in Pt Nanoparticle/Mesoporous CeO ₂ Catalyst: In Situ X-ray Spectroscopy and Diffraction Studies under Redox (H ₂ and O ₂ ) Atmospheres Alayoglu, Selim; An, Kwangjin; Melaet, Gérôme The Journal of Physical Chemistry C, Vol. 117, Issue 50 https://doi.org/10.1021/jp407280e	journal	December 2013
Probing Metal−Support Interactions under Oxidizing and Reducing Conditions: In Situ Raman and Infrared Spectroscopic and Scanning Transmission Electron Microscopic−X-ray Energy-Dispersive Spectroscopic Investigation of Supported Platinum Catalysts Lin, Wenyong; Herzing, A. A.; Kiely, C. J. The Journal of Physical Chemistry C, Vol. 112, Issue 15 https://doi.org/10.1021/jp710591m	journal	April 2008
Catalyst support effects on hydrogen spillover Karim, Waiz; Spreafico, Clelia; Kleibert, Armin Nature, Vol. 541, Issue 7635 https://doi.org/10.1038/nature20782	journal	January 2017
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
Structural evolution of atomically dispersed Pt catalysts dictates reactivity DeRita, Leo; Resasco, Joaquin; Dai, Sheng Nature Materials, Vol. 18, Issue 7 https://doi.org/10.1038/s41563-019-0349-9	journal	April 2019
Dynamic charge and oxidation state of Pt/CeO2 single-atom catalysts Daelman, Nathan; Capdevila-Cortada, Marçal; López, Núria Nature Materials, Vol. 18, Issue 11 https://doi.org/10.1038/s41563-019-0444-y	journal	August 2019
Reactivity of atomically dispersed Pt ²⁺ species towards H ₂ : model Pt–CeO ₂ fuel cell catalyst Lykhach, Yaroslava; Figueroba, Alberto; Camellone, Matteo Farnesi Physical Chemistry Chemical Physics, Vol. 18, Issue 11 https://doi.org/10.1039/C6CP00627B	journal	January 2016
The selection of experimental conditions in temperature-programmed reduction experiments Malet, Pilar; Caballero, Alfonso Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 84, Issue 7 https://doi.org/10.1039/f19888402369	journal	January 1988
Exceptional Activity for Methane Combustion over Modular Pd@CeO2 Subunits on Functionalized Al2O3 Cargnello, M.; Jaen, J. J. D.; Garrido, J. C. H. Science, Vol. 337, Issue 6095 https://doi.org/10.1126/science.1222887	journal	August 2012
Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R. Science, Vol. 341, Issue 6147 https://doi.org/10.1126/science.1240148	journal	July 2013
Activation of surface lattice oxygen in single-atom Pt/CeO ₂ for low-temperature CO oxidation Nie, Lei; Mei, Donghai; Xiong, Haifeng Science, Vol. 358, Issue 6369 https://doi.org/10.1126/science.aao2109	journal	December 2017

Similar Records

Does H₂ Temperature–Programmed Reduction Always Probe Solid–State Redox Chemistry? The Case of Pt/CeO₂

Journal Article · 2024 · Angewandte Chemie (International Edition) · OSTI ID:2564905

Lee, Jaeha; Christopher, Phillip

Tailoring the Local Environment of Platinum in Single‐Atom Pt ₁ /CeO ₂ Catalysts for Robust Low‐Temperature CO Oxidation

Journal Article · 2021 · Angewandte Chemie · OSTI ID:1819967

Jiang, Dong; Yao, Yonggang; Li, Tangyuan; +13 more

Effect of pretreatment conditions on acidity and dehydration activity of CeO₂-MeO_x catalysts

Journal Article · 2020 · Applied Catalysis. A, General · OSTI ID:1756860

Gnanamani, Muthu Kumaran; Garcia, Richard; Jacobs, Gary; +4 more

Title: Does H 2 Temperature‐Programmed Reduction Always Probe Solid‐State Redox Chemistry? The Case of Pt/CeO 2

Citation Formats

References (45)

Similar Records

Related Subjects

Title: Does H ₂ Temperature‐Programmed Reduction Always Probe Solid‐State Redox Chemistry? The Case of Pt/CeO ₂