Reactivity of O2 on Pd/Ru(0001) and PdRu/Ru(0001) surface alloys

Farı́as, Daniel; Minniti, Marina; Miranda, Rodolfo

doi:10.1063/1.4983994

Cited by 4 publications

(5 citation statements)

References 46 publications

(79 reference statements)

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“…A monolayer of Pd on Ru(0001) is more inert than Pd(111) . This was attributed to both compressive strain and charge transfer.…”

Section: Mechanisms and Barriers For O2 Dissociationmentioning

confidence: 99%

“…However, W does not form an oxide as easily as some other metals. Ru(0001) is quite reactive toward O 2 , and covering 95% of the surface with Pd only decreases the reactivity by a small amount …”

Section: Mechanisms and Barriers For O2 Dissociationmentioning

confidence: 99%

“…460 A monolayer of Pd on Ru(0001) is more inert than Pd (111). 461 This was attributed to both compressive strain and charge transfer. However, most studies of bimetallics suggest that orbital overlap is a more relevant and useful concept than charge transfer, where increased overlap between an atom and its neighbors tends to passivate the atom.…”

Section: Mechanisms and Barriers For O 2 Dissociationmentioning

confidence: 99%

“…Ru(0001) is quite reactive toward O 2 , and covering 95% of the surface with Pd only decreases the reactivity by a small amount. 461 The oxidation of these surfaces typically starts with O 2 activation, and the formation of O chemisorbed on the surface, followed quickly by the formation of a surface and then bulk oxide. 498−500 Surface oxidation of Ti(0001) occurs at 90 K, 501 Re forms a surface oxide at room temperature, 502 and Fe oxidizes very quickly at room temperature.…”

Section: Mechanisms and Barriers For O 2 Dissociationmentioning

confidence: 99%

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O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

et al. 2017

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The activation of O on metal surfaces is a critical process for heterogeneous catalysis and materials oxidation. Fundamental studies of well-defined metal surfaces using a variety of techniques have given crucial insight into the mechanisms, energetics, and dynamics of O adsorption and dissociation. Here, trends in the activation of O on transition metal surfaces are discussed, and various O adsorption states are described in terms of both electronic structure and geometry. The mechanism and dynamics of O dissociation are also reviewed, including the importance of the spin transition. The reactivity of O and O toward reactant molecules is also briefly discussed in the context of catalysis. The reactivity of a surface toward O generally correlates with the adsorption strength of O, the tendency to oxidize, and the heat of formation of the oxide. Periodic trends can be rationalized in terms of attractive and repulsive interactions with the d-band, such that inert metals tend to feature a full d band that is low energy and has a large spatial overlap with adsorbate states. More open surfaces or undercoordinated defect sites can be much more reactive than close-packed surfaces. Reactions between O and other species tend to be more prevalent than reactions between O and other species, particularly on more reactive surfaces.

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“…A monolayer of Pd on Ru(0001) is more inert than Pd(111) . This was attributed to both compressive strain and charge transfer.…”

Section: Mechanisms and Barriers For O2 Dissociationmentioning

confidence: 99%

Section: Mechanisms and Barriers For O2 Dissociationmentioning

confidence: 99%

Section: Mechanisms and Barriers For O 2 Dissociationmentioning

confidence: 99%

Section: Mechanisms and Barriers For O 2 Dissociationmentioning

confidence: 99%

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O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

et al. 2017

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“…Under normal conditions, both surface strain and ligand effects simultaneously modify the electronic structure and chemical properties of bimetallic surfaces. Consequently, extensive experimental and theoretical investigations have been conducted to examine their influence on reactivity. − …”

mentioning

confidence: 99%

Charge-Transfer-Controlled Quantum Dynamics of HCl Dissociation on the Ag/Au(111) Bimetallic Alloy Surface

Liu,

Peng,

et al. 2023

J. Phys. Chem. Lett.

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Understanding polar molecule dynamics on bimetallic surfaces, especially electropositivity and electronegativity, remains a challenge. Here, we report the reactivity of HCl on a strained Ag monolayer on Au(111) using sixdimensional quantum dynamics with a new machine-learning-based potential energy surface. Surprisingly, HCl reactivity is significantly suppressed by the Ag−Au interaction despite a lower HCl+Ag/Au(111) barrier than pure Ag(111). This arises from charge transfer between Ag and Au, where electronegative Au makes the top Ag layer on Ag/Au(111) electropositive, unlike that on pure Ag(111). Electropositive Ag in HCl+Ag/Au(111) attracts Cl, yielding an unfavorable H−Cl configuration and reduced reactivity. These findings deepen our understanding of polar molecule interactions on bimetallic surfaces, highlighting the role of charge transfer in dissociative chemisorption and the implications for catalyst design in heterogeneous catalysis.

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Quantum dynamics reveal different ligand effects by vibrational excitation in the dissociative chemisorption of HCl on the Au/Ag(111) surface

Liu

Shi

et al. 2022

The Journal of Chemical Physics

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The reactivity and selectivity of bimetallic surfaces are of fundamental importance in industrial applications. Here, we report the first six-dimensional (6D) quantum dynamics study for the role of surface strain and ligand effects on the reactivity of HCl on a strained pseudomorphic monolayer of Au deposited onto a Ag(111) substrate, with the aid of accurate machine learning-based potential energy surfaces. The substitute of Au into Ag changes the location of transition state, but the static barrier height remains roughly the same as pure Au(111).The 6D quantum dynamics calculations reveal the surface strain due to lattice expansion slightly enhances the reactivity. The ligand effect due to electronic structure interactions between Au and Ag substantially suppresses the reactivity of HCl in the ground vibrational state, but promotes the reactivity via vibrational excitation at high kinetic energies. This finding can be attributed to more close interaction with Ag atoms at the transition state close to the fcc site, as well as tight transition-state region making the vibrational excitation highly efficient in enhancing the reactivity. Our study quantitatively unravels the dynamical origin of reactivity control by two metals, which will ultimately provide valuable insight into the selectivity of catalyst.

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Reactivity of O2 on Pd/Ru(0001) and PdRu/Ru(0001) surface alloys

Cited by 4 publications

References 46 publications

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Charge-Transfer-Controlled Quantum Dynamics of HCl Dissociation on the Ag/Au(111) Bimetallic Alloy Surface

Quantum dynamics reveal different ligand effects by vibrational excitation in the dissociative chemisorption of HCl on the Au/Ag(111) surface

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Reactivity of O2 on Pd/Ru(0001) and PdRu/Ru(0001) surface alloys

Cited by 4 publications

References 46 publications

O2Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

O2Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Charge-Transfer-Controlled Quantum Dynamics of HCl Dissociation on the Ag/Au(111) Bimetallic Alloy Surface

Quantum dynamics reveal different ligand effects by vibrational excitation in the dissociative chemisorption of HCl on the Au/Ag(111) surface

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Product

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O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts