Interplay of Electronic Structure and Atomic Mobility in Nanoalloys of Au and Pt

Leppert, Linn; Albuquerque, Rodrigo Q.; Foster, Adam S.; Kümmel, Stephan

doi:10.1021/jp404341v

Cited by 31 publications

(45 citation statements)

References 57 publications

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“…[3][4]29 In addition to the impact of the catalyst composition on the onset potential, kinetic of the glycerol electro-oxidation was also influenced by the Ag addition to the AuAg catalyst (Fig. S2).…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Impact of the AuAg NPs Composition on Their Structure and Properties: A Theoretical and Experimental Investigation

et al. 2014

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Bimetallic AuAg NPs (NPs) were synthesized via chemical reduction of AuCl 3 and AgNO 3 and fully characterized by several experimental techniques and theoretical calculations. The plasmon absorptions of these NPs were correlated with the most stable particle structure through different simulations, revealing the most stable structure to be consisted of a gold core and a silver shell. This structural motif was then confirmed by HR-TEM coupled with line-scan EDS and molecular dynamics. Finally, the impact of the nanoparticle composition on their catalytic performance for glycerol electro-oxidation was evaluated. The better catalytic performance in terms of the onset potential found for the Au 50 Ag 50 and Au 75 Ag 25 catalysts suggests the existence of a synergistic effect between Au and Ag.

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Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Impact of the AuAg NPs Composition on Their Structure and Properties: A Theoretical and Experimental Investigation

et al. 2014

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“…We then calculate the electronic structure of representative subsystems with DFT. In particular, we focus on the calculated density of states (DOS) close to the Fermi edge as a general indicator for the chemical activity of the nanoparticle 19,21,30 . We separate the influence of the support on the electronic structure of the nanoparticle by explicitly calculating the DOS for the combined Pd@SiCN and contrast it with pure Pd and pure SiCN of the same geometry.…”

Section: Motivationmentioning

confidence: 99%

Investigating the electronic structure of a supported metal nanoparticle: Pd in SiCN

Schmidt

Albuquerque

Kempe

et al. 2016

Phys. Chem. Chem. Phys.

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We investigate the electronic structure of a Palladium nanoparticle that is partially embedded in a matrix of silicon carbonitride. From classical molecular dynamics simulations we first obtain a representative atomic structure. This geometry then serves as input to density-functional theory calculations that allow us to access the electronic structure of the combined system of particle and matrix. In order to make the computations feasible, we devise a subsystem strategy for calculating the relevant electronic properties. We analyze the Kohn-Sham density of states and pay particular attention to d-states which are prone to be affected by electronic self-interaction. We find that the density of states close to the Fermi level is dominated by states that originate from the Palladium nanoparticle. The matrix has little direct effect on the electronic structure of the metal. Our results contribute to explaining why silicon carbonitride does not have detrimental effects on the catalytic properties of palladium particles and can serve positively as a stabilizing mechanical support. MotivationFirst-principles electronic-structure theory 1-13 allows to gain unbiased insights into the microscopic, quantum-mechanical effects that are at the heart of modern nanotechnology [14][15][16][17][18][19][20][21][22][23][24] . However, often full ab-initio studies on systems of experimental relevance remain challenging since the computational effort grows immensely with system size 25 . For instance, in many experiments metal nanoparticles that have a diameter of several nm and contain several hundreds or thousands of atoms are used. For such systems, tens of thousands of electrons have to be taken into account for first-principles studies. Even with modern computers using massive parallelization, geometry optimizations and detailed investigations of the electronic structure of systems of that size are out of reach. Therefore, strategies have to be devised how insights can be gained into large systems despite of these computational limitations. In this work, we take a first step in this direction and investigate a palladium nanoparticle which is partially embedded in a matrix of silicon carbonitride (SiCN).This system is of practical relevance because noble-metal nanoparticles, in particular nanoparticles containing Pd, are effective catalysts for a wide range of chemical reactions [26][27][28][29][30] . In comparison to bulk metals, nanoparticles exhibit a high surface-

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“…In recent years, it has particularly often been relied on in studies of clusters [92][93][94][95][96][97][98][99][100][101][102][103][104]. Many of the potentially technologically relevant clusters contain elements with d-electrons.…”

Section: Introductionmentioning

confidence: 99%

The Influence of One-Electron Self-Interaction on d-Electrons

Schmidt

Kümmel

2016

Computation

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Abstract:We investigate four diatomic molecules containing transition metals using two variants of hybrid functionals. We compare global hybrid functionals that only partially counteract self-interaction to local hybrid functionals that are designed to be formally free from one-electron self-interaction. As d-orbitals are prone to be particularly strongly influenced by self-interaction errors, one may have expected that self-interaction-free local hybrid functionals lead to a qualitatively different Kohn-Sham density of states than global hybrid functionals. Yet, we find that both types of hybrids lead to a very similar density of states. For both global and local hybrids alike, the intrinsic amount of exact exchange plays the dominant role in counteracting electronic self-interaction, whereas being formally free from one-electron self-interaction seems to be of lesser importance.

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Interplay of Electronic Structure and Atomic Mobility in Nanoalloys of Au and Pt

Cited by 31 publications

References 57 publications

Impact of the AuAg NPs Composition on Their Structure and Properties: A Theoretical and Experimental Investigation

Impact of the AuAg NPs Composition on Their Structure and Properties: A Theoretical and Experimental Investigation

Investigating the electronic structure of a supported metal nanoparticle: Pd in SiCN

The Influence of One-Electron Self-Interaction on d-Electrons

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