The Synergy of Dilute Pd and Surface Oxygen Species for Methane Upgrading on Au<sub>3</sub>Pd(111)

Quan, K.; Tran, Hung-Vu; Wang, Shengguang; Grabow, Lars C.

doi:10.1002/ente.201900732

Cited by 3 publications

(3 citation statements)

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“…The calculation results show that on the alloy surface Au 3 Pd(111), the hydrogen affinity difference is −1.33 eV (more negative than −0.64 eV), which means that the pre‐adsorbed oxygen atom can strongly help to abstract the hydrogen atom. The mechanisms of methane dissociation on Au 3 Pd(111) are named as the Au pathway (i.e., CH 3 binds with the atop Au) and the Pd pathway (i.e., CH 3 binds with the atop Pd) 58 . Following the Au pathway, the activation energies of the oxygen‐assisted dissociation and the direct dissociation are 1.42 and 1.92 eV.…”

Section: Resultsmentioning

confidence: 99%

Mechanisms of CH₄ activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations

Wang,

Wang

2023

J Comput Chem

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The chemisorbed oxygen usually promotes the CH bond activation over less active metals like IB group metals but has no effect or even an inhibition effect over more active metals like Pd based on the static electronic structure study. However, the understanding in terms of dynamics knowledge is far from complete. In the present work, methane dissociation on the oxygen‐preadsorbed transition metals including Au, Cu, Ni, Pt, and Pd is systemically studied by reactive force field (ReaxFF). The ReaxFF simulation results indicate that CH4 molecules mainly undergo the direct dissociation on Ni, Pt, and Pd surfaces, while undergo the oxygen‐assisted dissociation on Au and Cu surfaces. Additionally, the ab initio molecular dynamics (AIMD) simulations with the umbrella sampling are employed to study the free‐energy changes of CH4 dissociation, and the results further support the CH4 dissociation pathway during the ReaxFF simulations. The present results based on ReaxFF and AIMD will provide a deeper dynamic understanding of the effects of pre‐adsorbed oxygen species on the CH bond activation compared to that of static DFT.

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Section: Resultsmentioning

confidence: 99%

Mechanisms of CH₄ activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations

Wang,

Wang

2023

J Comput Chem

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“…C–H bond activation and the DH process on transition-metal (TM) surfaces have been widely investigated for light alkanes, both experimentally and theoretically. For instance, the activation of methane under moderate conditions was only observed on oxygen-precovered Cu surfaces, and using density functional theory (DFT) calculations, it was shown that the activation energy of methane is decreased using promoters such as O*, OH*, O 2 *, and OCH 3 . − Promoters for methane activation have also been evaluated on Pd and Au as well as their alloys. , Alkane DH has been studied primarily on Pt catalysts for the nonoxidative process, and investigations targeted Ni and Pd for the ODH process. ,,− The direct dissociative chemisorption of propane and iso-butane and their fully deuterated isotopes was studied on the Pt(110) surface, where it was found that the difference in activation energies of C–H and C–D bond cleavage can be attributed to differences in zero-point energy stemming from the two isotopes. − …”

Section: Introductionmentioning

confidence: 99%

“…18−21 Promoters for methane activation have also been evaluated on Pd and Au as well as their alloys. 22,23 Alkane DH has been studied primarily on Pt catalysts for the nonoxidative process, and investigations targeted Ni and Pd for the ODH process. 10,13,24−34 The direct dissociative chemisorption of propane and iso-butane and their fully deuterated isotopes was studied on the Pt(110) surface, where it was found that the difference in activation energies of C−H and C−D bond cleavage can be attributed to differences in zeropoint energy stemming from the two isotopes.…”

Section: Introductionmentioning

confidence: 99%

Trends in the Activation of Light Alkanes on Transition-Metal Surfaces

et al. 2020

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The first (oxidative) dehydrogenation step of light alkanes (ethane, propane, and n-butane) on transition-metal (closed-packed and stepped) surfaces is analyzed using density functional theory (DFT) calculations. It is shown that the transition-state energies (ΔE TS) of the C–H bond activation scale linearly with the corresponding final-state energies (ΔE FS), and all alkanes studied here share the same linear scaling relationships for the nonoxidative, oxygen-assisted, and hydroxyl-assisted reactions. Variations in ΔE TS between alkanes can be mainly attributed to differences in dispersion contributions determined by the carbon-chain length. As the carbon chain increases, the ΔE TS of the alkane C–H bond activation decreases. In addition, the ΔE TS of the first (O)DH step of propane and n-butane is linearly correlated with the ΔE TS of the first ethane (O)DH step. We also find that the oxygen and hydroxyl adsorption energies on the transition-metal surfaces (closed-packed and stepped) are dictating the promoting/poisoning effect of the C–H bond activation. Based on our extensive DFT calculations, we find that Pt has the lowest C–H bond transition-state energy for both the nonoxidative and oxidative pathways, and metals such as Au and Ag become active for C–H bond activation of alkanes only when oxygen and hydroxyl species are present on the metal surfaces. Finally, by establishing scaling relationships over a wide range of transition-metal surfaces, we have developed a simple and highly accurate model for the prediction of C–H bond activation barriers for the (oxidative) dehydrogenation of light alkanes.

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Coupling the chemical reactivity of bimetallic surfaces to the orientations of liquid crystals

Szilvási

Gold

et al. 2021

Mater. Horiz.

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The Synergy of Dilute Pd and Surface Oxygen Species for Methane Upgrading on Au₃Pd(111)

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record. Please cite this article as

Cited by 3 publications

References 75 publications

Mechanisms of CH₄ activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations

Mechanisms of CH₄ activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations

Trends in the Activation of Light Alkanes on Transition-Metal Surfaces

Coupling the chemical reactivity of bimetallic surfaces to the orientations of liquid crystals

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The Synergy of Dilute Pd and Surface Oxygen Species for Methane Upgrading on Au3Pd(111)

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record. Please cite this article as

Cited by 3 publications

References 75 publications

Mechanisms of CH4 activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations

Mechanisms of CH4 activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations

Trends in the Activation of Light Alkanes on Transition-Metal Surfaces

Coupling the chemical reactivity of bimetallic surfaces to the orientations of liquid crystals

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Product

Resources

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The Synergy of Dilute Pd and Surface Oxygen Species for Methane Upgrading on Au₃Pd(111)

Mechanisms of CH₄ activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations

Mechanisms of CH₄ activation over oxygen‐preadsorbed transition metals by ReaxFF and AIMD simulations