Insights and comparison of structure–property relationships in propane and propene catalytic combustion on Pd- and Pt-based catalysts

Yang, An‐Chih; Streibel, Verena; Choksi, Tej S.; Aljama, Hassan; Werghi, Baraa; Bare, Simon R.; Sánchez‐Carrera, Roel S.; Schäfer, Ansgar; Li, Yuejin; Abild‐Pedersen, Frank; Cargnello, Matteo

doi:10.1016/j.jcat.2021.06.018

Cited by 30 publications

(25 citation statements)

References 68 publications

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“…(c) Reaction order vs temperature: Propene and oxygen are predicted to have a negative and positive reaction order, respectively. This prediction in reaction orders is in agreement with experimental results …”

Section: Resultssupporting

confidence: 92%

“…For this model, we obtain a reaction order that is consistently positive for oxygen and negative for propene across the considered temperature range (see Figure c). This finding is in agreement with the experimental reaction order measurements . Given the propene-fragment-covered surface and the lack of oxygen apparent from the coverage plot, these reaction orders are in agreement with the corresponding coverage plot in Figure a.…”

Section: Resultssupporting

confidence: 90%

“…The reaction orders are near zero for propene and oxygen at low temperatures and obtain slightly positive values for oxygen at higher temperatures. This result is in slight disagreement with experiment, where we had observed positive orders for oxygen and negative orders for propene . The model with an oxygen reservoir site, however, cannot replicate these reaction order trends since it does not include the competition between oxygen and propene for surface sites.…”

Section: Resultscontrasting

confidence: 82%

“…(2) At the oxygen coverage determined by the thermodynamics, propene fragments adsorb more favorably, thus poisoning free sites and leading to a lack of oxygen to drive complete combustion. This propene poisoning explains the experimentally determined negative reaction order observed for propene and the positive reaction order for oxygen.…”

Section: Resultsmentioning

confidence: 64%

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Microkinetic Modeling of Propene Combustion on a Stepped, Metallic Palladium Surface and the Importance of Oxygen Coverage

et al. 2022

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Better emission control of internal combustion engines can be achieved by more efficient catalytic hydrocarbon combustion at low temperatures. For a knowledge-based design of suitable catalyst candidates, a promising approach integrates theoretical models with experimental benchmarks. Studying catalytic hydrocarbon combustion theoretically is challenging, however, since hydrocarbon reaction networks are complex: even simple C2 combustion reactions include hundreds of possible elementary steps. Herein, we present a paradigm to address this challenge by (1) supplementing experimental insights with extensive density functional theory studies to derive a proxy combustion reaction network; (2) using machine learning-enhanced transition state search to rigorously scan reaction coordinates; and (3) combining ab initio thermodynamics, microkinetic modeling, and a degree of rate control analysis to unveil adsorbate coverage effects and rate-limiting reaction steps. Our systematic approach permits modeling a reaction as complex as propene combustion on palladium while maintaining the computationally efficient mean-field approximation. Using a partially oxygen-covered palladium surface model, which includes adsorbate–adsorbate interactions, we predict experimentally measured rates within 2 orders of magnitude without parameter fitting. The corresponding degree of rate control analysis yields that the second and penultimate dehydrogenation step in the reaction network limit the rate of propene combustion on palladium.

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Section: Resultssupporting

confidence: 92%

Section: Resultssupporting

confidence: 90%

Section: Resultscontrasting

confidence: 82%

Section: Resultsmentioning

confidence: 64%

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Microkinetic Modeling of Propene Combustion on a Stepped, Metallic Palladium Surface and the Importance of Oxygen Coverage

et al. 2022

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“…These trends are consistent with the results obtained for C 2 H 4 oxidation on Pt and Pd wires. However, this result here may be different from that reported by Yang et al,74 who have recently studied the catalytic oxidation of C 3 H 6 over Pt and Pd and the combination of both metals supported on Al 2 O 3 . They found the higher catalytic performance in the case of Pt/Pd, then Pt cases.…”

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confidence: 99%

Comparative Study of the Catalytic Oxidation of Hydrocarbons on Platinum and Palladium Wires and Nanoparticles

et al. 2022

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This paper presents a comparative experimental study of the oxidation of light alkanes (methane and ethane) and alkenes (ethylene and propylene) catalyzed by unsupported platinum (Pt) and palladium (Pd). The oxidation was studied under a wide range of reaction conditions, such as temperatures, residence times, and mixture equivalence ratios. Two different catalyst morphologies were investigated: a packed bed of nanoparticles and a wire coiled inside a tube reactor. The order of hydrocarbons in terms of their oxidation activity on the Pt and Pd was found to be consistent regardless of the wire/nanoparticle morphology, with propylene exhibiting the highest reactivity followed by ethylene, ethane, and then methane. The effects of residence time on the oxidation of hydrocarbons showed similar trends with the two types of catalysts, whereby a longer residence time leads to a higher oxidation activity. However, the degree of that activity enhancement was insignificant with the nanoparticles. On the other hand, the effects of the equivalence ratio, φ, were significantly different between the two catalyst configurations. In the near-adiabatic wire reactor, the oxidation activity increases with increasing φ due to the heat release and higher temperature ramp along the reactor. The reverse is true in the isothermal bed of nanoparticles. Analysis of the surface of the catalyst using X-ray diffraction revealed that for the palladium, palladium oxide was active in promoting the oxidation of all tested hydrocarbons at a lower temperature than platinum. That was not the case for nanoparticles, as the temperature was not sufficiently high to oxidize the surface. The obtained results help understand the catalytic oxidation of the tested hydrocarbons under different conditions and help optimize the operation parameters for catalysts.

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On the Structure Insensitivity of Propane Total Oxidation over Pt/CeO₂: A Comparison between Single Atoms, Clusters and Nanoparticles

Gao,

Zhang,

Wang

et al. 2023

ChemCatChem

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A series of Pt/CeO2 catalysts with varied sizes of Pt domains are prepared and evaluated in propane total oxidation reaction, to investigate the structural sensitivity regarding the particle sizes and metal‐support interactions. Over Pt single atoms, clusters or nanoparticles (NP), the obtained similar turnover frequencies and apparent activation energies suggest the reaction is structure insensitive to the sizes of Pt domains. Nonetheless, detailed kinetic study reveals different adsorption behavior of reactants (C3H8 and O2) over these Pt species. Following a Langmuir‐Hinshelwood mechanism, C3H8 and O2 competitively adsorb on Pt surface. The adsorption of C3H8 and O2 on Pt single atom is much easier than on Pt nanoparticles due to its lower coordination. These findings provide experimental evidences for the reaction behavior of C3H8 oxidation over Pt/CeO2 catalysts, and lay a foundation for further understanding of the structure‐property relationship.

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Insights and comparison of structure–property relationships in propane and propene catalytic combustion on Pd- and Pt-based catalysts

Cited by 30 publications

References 68 publications

Microkinetic Modeling of Propene Combustion on a Stepped, Metallic Palladium Surface and the Importance of Oxygen Coverage

Microkinetic Modeling of Propene Combustion on a Stepped, Metallic Palladium Surface and the Importance of Oxygen Coverage

Comparative Study of the Catalytic Oxidation of Hydrocarbons on Platinum and Palladium Wires and Nanoparticles

On the Structure Insensitivity of Propane Total Oxidation over Pt/CeO₂: A Comparison between Single Atoms, Clusters and Nanoparticles

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Insights and comparison of structure–property relationships in propane and propene catalytic combustion on Pd- and Pt-based catalysts

Cited by 30 publications

References 68 publications

Microkinetic Modeling of Propene Combustion on a Stepped, Metallic Palladium Surface and the Importance of Oxygen Coverage

Microkinetic Modeling of Propene Combustion on a Stepped, Metallic Palladium Surface and the Importance of Oxygen Coverage

Comparative Study of the Catalytic Oxidation of Hydrocarbons on Platinum and Palladium Wires and Nanoparticles

On the Structure Insensitivity of Propane Total Oxidation over Pt/CeO2: A Comparison between Single Atoms, Clusters and Nanoparticles

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Product

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On the Structure Insensitivity of Propane Total Oxidation over Pt/CeO₂: A Comparison between Single Atoms, Clusters and Nanoparticles