Quantifying interactions on interfaces between metal particles and oxide supports in catalytic nanomaterials

Neyman, Konstantin M.; Kozlov, Sergey M.

doi:10.1038/s41427-022-00405-4

Cited by 16 publications

(11 citation statements)

References 33 publications

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“…Since employing realistic NP models is well-known to be extremely important for accurate description of nanostructured materials in simulations, [39,40] various approaches were proposed to obtain representative models of the NPs prepared through the gas-phase synthesis. [41,42] For example, the kinetic Monte Carlo model developed by Davari and Mukherjee [43] describes the gas-phase nucleation of metallic NPs.…”

Section: Introductionmentioning

confidence: 99%

Cu–Au nanoparticles produced by the aggregation of gas‐phase metal atoms for CO oxidation

et al. 2022

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Alloy nanoparticles (nanoalloys) are widely applied in heterogeneous catalysts, advanced electrodes, biomaterials, and other areas. The properties of nanoalloys can be tuned to a significant extent by their structures and compositions, which are governed by the employed synthetic procedure. Often such synthesis occurs in non‐equilibrium conditions and yields nanoalloys with structures and properties that are different from those obtained in thermodynamic equilibrium. In this work, we characterize how the non‐equilibrium conditions during the synthesis of Cu–Au alloys via physical vapor deposition (PVD) affect their morphology, composition, electronic structure, and reactivity in CO oxidation. We used molecular dynamics to simulate the PVD synthesis of Cu–Au nanoalloys through the non‐isothermal aggregation of Cu and Au atoms at a 3:1 ratio in the Ar atmosphere to obtain realistic structures of Cu–Au nanoparticles. Due to the different aggregation kinetics of Au and Cu atoms, the average Au concentration in the obtained Cu–Au particles varied between 14% and 50% depending on the nanoparticle size and the aggregation time. Density functional simulations revealed that the reactivity of the obtained Cu–Au clusters toward CO and oxygen as well as Brønsted–Evans–Polanyi relations for CO oxidation significantly depend on whether the clusters had fcc, icosahedral, or amorphous structures and do not strongly correlate with the d‐band centers of the adsorption sites. Our study highlights the importance of the non‐equilibrium character of nanoalloy structure and composition for their electronic structure and catalytic properties. The performed analysis of the reactivity of Cu–Au clusters with realistic structures in CO oxidation will help the optimization of Cu–Au catalysts for this societally important reaction.

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Section: Introductionmentioning

confidence: 99%

Cu–Au nanoparticles produced by the aggregation of gas‐phase metal atoms for CO oxidation

et al. 2022

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“…Although charge transfer is considered to be one of the most important components of metal-oxide interactions, 92,93 its value is calculated to be negligible for pristine ZnO lms supported on all considered metals (Table S4 †). At the same time, ZnO lms are calculated to change the work function of metal supports by 0.1-0.4 eV, which indicates signicant charge polarization on the metal-oxide interfaces (Table S5 †).…”

Section: Electronic Structure Of Supported Zno Lmsmentioning

confidence: 99%

Tunable properties and composition of ZnO films supported on metal surfaces

2023

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“…EMSI are exhibited by various combinations of supports and metals, − among which ceria-supported transition metals are frequently explored. − Transition-metal particles often become somewhat oxidized upon contact with a reducible support such as ceria, which can affect adsorption energies and dissociation barriers of key steps within a reaction mechanism. EMSI are also markedly size-dependent, with large particles, clusters, and single atoms exhibiting different propensity for oxidation. ,− Despite recent work elucidating some aspects of EMSI, the stability of different electronic states and the effect of the oxidation state of supported metal particles on their chemical reactivity and catalytic properties are generally not well understood.…”

Section: Introductionmentioning

confidence: 99%

Systematic Characterization of Electronic Metal–Support Interactions in Ceria-Supported Pt Particles

Castro-Latorre,

Neyman,

Bruix

2023

J. Phys. Chem. C

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Electronic metal−support interactions affect the chemical and catalytic properties of metal particles supported on reducible metal oxides, but their characterization is challenging due to the complexity of the electronic structure of these systems. These interactions often involve different states with varying numbers and positions of strongly correlated d or f electrons and the corresponding polarons. In this work, we present an approach to characterize electronic metal− support interactions by means of computationally efficient density functional calculations within the projector augmented wave method. We describe Ce 3+ cations with potentials that include a Ce4f electron in the frozen core, overcoming prevalent convergence and 4f electron localization issues. We systematically explore the stability and chemical properties of different electronic states for a Pt 8 /CeO 2 (111) model system, revealing the predominant effect of electronic metal−support interactions on Pt atoms located directly at the metal−oxide interface. Adsorption energies and the reactivity of these interface Pt atoms vary significantly upon donation of electrons to the oxide support, pointing to a strategy to selectively activate interfacial sites of metal particles supported on reducible metal oxides.

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Quantifying interactions on interfaces between metal particles and oxide supports in catalytic nanomaterials

Cited by 16 publications

References 33 publications

Cu–Au nanoparticles produced by the aggregation of gas‐phase metal atoms for CO oxidation

Cu–Au nanoparticles produced by the aggregation of gas‐phase metal atoms for CO oxidation

Tunable properties and composition of ZnO films supported on metal surfaces

Systematic Characterization of Electronic Metal–Support Interactions in Ceria-Supported Pt Particles

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