States of Pt/CeO2 catalysts for CO oxidation below room temperature

Slavinskaya, Elena M.; Stadnichenko, A. I.; Domínguez, Jon Eunan Quinlivan; Стонкус, О. А.; Vorokhta, Mykhailo; Castro-Latorre, Pablo; Bruix, Albert; Neyman, Konstantin M.; Boronin, Andrei I.

doi:10.1016/j.jcat.2023.03.004

Cited by 18 publications

(12 citation statements)

References 66 publications

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“…We note that with the increasing temperature of the catalyst during CO oxidation, additional channels of CO 2 formation will be opened, including the Mars–van Krevelen mechanism 16–18 and the formation and decomposition of more stable tridentate carbonates A. These channels operate mostly above 400 K and may potentially trigger the reduction of ionic Pt species yielding Pt* aggregates and metallic Pt 0 NPs.…”

Section: Resultsmentioning

confidence: 95%

“…Since metallic Pt 0 NPs are not fully oxidized under realistic CO oxidation conditions, 17 we assume that the redox channel associated with CO spillover and formation of bidentate carbonates will play an important role in low-temperature CO oxidation.…”

Section: Resultsmentioning

confidence: 99%

“…Since metallic Pt 0 NPs are not fully oxidized under realistic CO oxidation conditions, 17 we assume that the redox channel…”

Section: Involvement Of Ceo 2 In Co Oxidation Reactionmentioning

confidence: 99%

“…It is known that the Pt undergoes dynamic structural transformations between these forms depending on the reaction conditions. 11,14,15 In recent studies by Boronin et al, [16][17][18] Pt-doped cerium oxide (Pt-CeO 2 ) showed exceptionally high catalytic activity for CO oxidation at temperatures below 273 K. The authors proposed an associative (concerted) mechanism that involves the reaction of weakly adsorbed O 2 and CO molecules at PtO x clusters on Ptdoped CeO 2 . The latter contained atomically dispersed Pt 2+ and Pt 4+ species.…”

Section: Introductionmentioning

confidence: 99%

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Probing the redox capacity of Pt–CeO₂ model catalyst for low-temperature CO oxidation

et al. 2023

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

“…Since metallic Pt 0 NPs are not fully oxidized under realistic CO oxidation conditions, 17 we assume that the redox channel…”

Section: Involvement Of Ceo 2 In Co Oxidation Reactionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Probing the redox capacity of Pt–CeO₂ model catalyst for low-temperature CO oxidation

et al. 2023

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“…In order to evaluate the stability of the Pt 10 (CO) 9 and Pt 8 (CO) 7 complexes deposited on the ceria (111) surface and Ce 21 O 42 nanoparticle models, respectively, we calculated the electronic and Gibbs free binding energies of each CO molecule at T = 0, 273.15, and 423.15 K and a CO partial pressure of 1013.25 Pa (0.01 atm) 43 (see Figure S4 and Table S7 in SI). All of the calculated values are exergonic, confirming that both investigated models are thermodynamically stable under the reaction conditions.…”

Section: Computational Methods and Modelsmentioning

confidence: 99%

Comparison of the Reactivity of Platinum Cations and Clusters Supported on Ceria or Alumina in Carbon Monoxide Oxidation

2023

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The mechanism of CO oxidation on platinum species supported on ceria or alumina was studied via periodic density functional calculations. In order to elucidate the nature of the catalytically active species, various reaction paths involving monoatomic species in different oxidation statesPt0, Pt2+, and Pt4+as well as platinum clusters were modelled. Since the oxygen centers that participate in the oxidation process may have diverse origins, the interaction of CO with the oxygen from the ceria support, dissociated O2 molecules on the platinum species, and the oxygen molecule healing the surface oxygen vacancy in the support was considered. Ceria was modeled both as a (111) surface and as a nanoparticle, and γ-alumina was modeled as a (001) surface. The reaction paths via complexes of Pt2+ and Pt4+ cations were found to have the lowest activation barriers, 22–35 kJ/mol. The calculated activation energies on platinum clusters with high CO coverage supported on the ceria surface and the nanoparticle are also low, 40 and 19 kJ/mol, respectively. The barriers are significantly higher, 90–120 kJ/mol, when the reaction occurs on platinum supported on γ-alumina or when an oxygen preadsorbed on the platinum cluster is involved in the process. The calculations allowed us to discriminate the role of the oxidant in the modeled reaction paths and to conclude that the activation barriers are low when the oxidants are platinum species and notably higher when the oxidants are Ce4+ cations.

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Low‐Temperature CO Oxidation by the Pt/CeO₂ Based Catalysts

Stadnichenko,

Slavinskaya,

Stonkus

et al. 2024

ChemCatChem

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This review analyzes the literature data and the results of studies of the Pt/CeO2‐based catalysts that are capable of providing the low‐temperature CO oxidation (LTO CO). The review summarizes the catalytic characteristics and the main properties of Pt/CeO2‐based catalysts necessary for the low‐temperature oxidation at T < 50 oC. Analysis of the literature data on the use of physical methods of investigation and their correlation with the activity of Pt/CeO2 catalysts allowed us to conclude that the main active forms of platinum are small metallic clusters, single atoms Pt2+‐SA and oxide clusters PtOx interacting with ceria nanoparticles. It has been established that the most active forms are PtOx clusters, which provide a high reaction rate in the temperature range from ‐50 to +50 °C. Forms of ionic Pt2+ with different coordination with oxygen ensure the activity of catalysts starting at temperatures above 100 °C. Finally, small metallic clusters occupy an intermediate position, providing activity above 0 °C, but their instability and gradual transition to the oxidized state Pt2+/PtOx are noted. At the conclusion of the review, the results of mathematical modeling demonstrate the correct kinetics description of the low‐temperature CO oxidation based on the Mars‐van Krevelen and associative mechanisms.

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States of Pt/CeO2 catalysts for CO oxidation below room temperature

Cited by 18 publications

References 66 publications

Probing the redox capacity of Pt–CeO₂ model catalyst for low-temperature CO oxidation

Probing the redox capacity of Pt–CeO₂ model catalyst for low-temperature CO oxidation

Comparison of the Reactivity of Platinum Cations and Clusters Supported on Ceria or Alumina in Carbon Monoxide Oxidation

Low‐Temperature CO Oxidation by the Pt/CeO₂ Based Catalysts

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States of Pt/CeO2 catalysts for CO oxidation below room temperature

Cited by 18 publications

References 66 publications

Probing the redox capacity of Pt–CeO2 model catalyst for low-temperature CO oxidation

Probing the redox capacity of Pt–CeO2 model catalyst for low-temperature CO oxidation

Comparison of the Reactivity of Platinum Cations and Clusters Supported on Ceria or Alumina in Carbon Monoxide Oxidation

Low‐Temperature CO Oxidation by the Pt/CeO2 Based Catalysts

Contact Info

Product

Resources

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Probing the redox capacity of Pt–CeO₂ model catalyst for low-temperature CO oxidation

Probing the redox capacity of Pt–CeO₂ model catalyst for low-temperature CO oxidation

Low‐Temperature CO Oxidation by the Pt/CeO₂ Based Catalysts