Γ-point density functional calculations on the adsorption of rhodium and palladium particles on MgO(001) surface and their reactivity

Stirling, András; Gunji, Isao; Endou, Akira; Oumi, Yasunori; Kubo, omoji; Miyamoto, Akira

doi:10.1039/a604388g

Cited by 32 publications

(17 citation statements)

References 18 publications

(3 reference statements)

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“…These results are in agreement with [5] [59] [60]. In general, a good agreement is established between the geometrical parameters obtained in this work and the reported theoretical values for Rh/MgO(001) surface (2.09 Å [61]) and for Pd/MgO(001) (2.15 Å [62]) at the low coordinated surface.…”

Section: Adsorption Of Single Pd and Rh Atomssupporting

confidence: 91%

Effect of Surface Site on the Spin State for the Interaction of NO with Pd2, Rh2 and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

Aal¹

2016

OJPC

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An attempt has been made to analyze the effect of surface site on the spin state for the interaction of NO with Pd 2 , Rh 2 and PdRh nanoparticles that supported at regular and defective MgO(001) surfaces. The adsorption properties of NO on homonuclear, Pd 2 , Rh 2 , and heteronuclear transition metal dimers, PdRh, that deposited on MgO(001) surface have been studied by means of hybrid density functional theory calculations and embedded cluster model. The most stable NO chemisorption geometry is in a bridge position on Pd 2 and a top configuration of Rh 2 and PdRh with N-down oriented. NO prefers binding to Rh site when both Rh and Pd atoms co-exist in the PdRh. The natural bond orbital analysis (NBO) reveals that the electronic structure of the adsorbed metal represents a qualitative change with respect to that of the free metal. The adsorption properties of NO have been analyzed with reference to the NBO, charge transfer, band gaps, pairwise and nonpairwise additivity. The binding of NO precursor is dominated by the () x M NO i E − pairwise additive components and the role of the support was not restricted to supporting the metal. The adsorbed dimers on the MgO surface lose most of the metal-metal interaction due to the relatively strong bond with the substrate. Spin polarized calculations were performed and the results concern the systems in their more stable spin states. Spin quenching occurs for Rh atom, Pd 2 , Rh 2 and PdRh complexes at the terrace and defective surfaces. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support and dimer-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals and dimers. Although the interaction of Pd, Rh, Pd 2 , Rh 2 and PdRh particles with Fs sites is much stronger than the regular sites O 2 − , the adsorption of NO is stronger when the particular dimers are supported on an anionic site than on an Fs site of the MgO(001). The encountered variations in magnetic properties of the adsorbed species at MgO(001) surface are S. A. Aal 2 correlated with the energy gaps of the frontier orbitals. The results show that the spin state of adsorbed metal atoms on oxide supports and the role of precursor molecules on the magnetic and binding properties of complexes need to be explicitly taken into account.

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Section: Adsorption Of Single Pd and Rh Atomssupporting

confidence: 91%

Effect of Surface Site on the Spin State for the Interaction of NO with Pd2, Rh2 and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

Aal¹

2016

OJPC

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“…2c). Among the precious metal atoms shown in Table 1, results for Rh and Pd systems are in good agreement with previous studies [43][44][45], thus indicating the validity of the calculated results. Type 1) in-plane and Type 2) perpendicular geometries (Fig.…”

Section: Precious Metal Catalysts For Deno Xsupporting

confidence: 89%

Combinatorial Computational Chemistry Approach for Materials Design:Applications in deNOx Catalysis, Fischer-Tropsch Synthesis, Lanthanoid Complex, and Lithium Ion Secondary Battery

Koyama¹,

Tsuboi²,

Endou³

et al. 2007

CCHTS

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Computational chemistry can provide fundamental knowledge regarding various aspects of materials. While its impact in scientific research is greatly increasing, its contributions to industrially important issues are far from satisfactory. In order to realize industrial innovation by computational chemistry, a new concept "combinatorial computational chemistry" has been proposed by introducing the concept of combinatorial chemistry to computational chemistry. This combinatorial computational chemistry approach enables theoretical high-throughput screening for materials design. In this manuscript, we review the successful applications of combinatorial computational chemistry to deNO(x) catalysts, Fischer-Tropsch catalysts, lanthanoid complex catalysts, and cathodes of the lithium ion secondary battery.

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“…This tendency can be compared with that obtained by Loffreda et al 32 Regarding the E ads of NO molecules on the Rh and Pd surfaces, they reported that the order was found to be Rh > Pd. Our earlier studies 34,50 also showed that the adsorption of the NO molecule on Rh was more preferable than that on Pd. Moreover, the present order of the absolute values of E ads of NO on the Rh and Pd clusters may be related to the efficiency of Rh for the SCR of NO x in TWC.…”

Section: Methods and Modelsmentioning

confidence: 85%

Comparative Investigation on the Adsorption Properties of Precious Metal Clusters toward NO: A Density Functional Study

et al. 2000

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The adsorption properties of precious metal clusters such as Rh, Pd, Ag, Ir, Pt, and Au toward NO were systematically investigated using the density functional calculations. It was found that the most energetically stable adsorption state of NO on the tetrahedral M 4 clusters was found to be the NO/Ir 4 system. The ability of the precious metal clusters to activate the N-O bond was also discussed mainly from a geometric point of view. The entire linear behavior of the elongation of the N-O bond of NO molecules adsorbed on M 4 clusters was observed with increasing values of the molecular charge on the NO molecules, which suggests the back-donation of an electron to the 2π* orbital of the NO molecules. The substantial elongation of the N-O bond was found on the NO/Ir 4 system, which was nearly equal to that on the NO/Rh 4 systems. These results indicate that the Ir cluster has the best properties for the adsorption and activation of NO.

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Γ-point density functional calculations on the adsorption of rhodium and palladium particles on MgO(001) surface and their reactivity

Cited by 32 publications

References 18 publications

Effect of Surface Site on the Spin State for the Interaction of NO with Pd<sub>2</sub>, Rh<sub>2</sub> and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

Effect of Surface Site on the Spin State for the Interaction of NO with Pd<sub>2</sub>, Rh<sub>2</sub> and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

Combinatorial Computational Chemistry Approach for Materials Design:Applications in deNOx Catalysis, Fischer-Tropsch Synthesis, Lanthanoid Complex, and Lithium Ion Secondary Battery

Comparative Investigation on the Adsorption Properties of Precious Metal Clusters toward NO: A Density Functional Study

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Γ-point density functional calculations on the adsorption of rhodium and palladium particles on MgO(001) surface and their reactivity

Cited by 32 publications

References 18 publications

Effect of Surface Site on the Spin State for the Interaction of NO with Pd&lt;sub&gt;2&lt;/sub&gt;, Rh&lt;sub&gt;2&lt;/sub&gt; and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

Effect of Surface Site on the Spin State for the Interaction of NO with Pd&lt;sub&gt;2&lt;/sub&gt;, Rh&lt;sub&gt;2&lt;/sub&gt; and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

Combinatorial Computational Chemistry Approach for Materials Design:Applications in deNOx Catalysis, Fischer-Tropsch Synthesis, Lanthanoid Complex, and Lithium Ion Secondary Battery

Comparative Investigation on the Adsorption Properties of Precious Metal Clusters toward NO: A Density Functional Study

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Effect of Surface Site on the Spin State for the Interaction of NO with Pd<sub>2</sub>, Rh<sub>2</sub> and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces

Effect of Surface Site on the Spin State for the Interaction of NO with Pd<sub>2</sub>, Rh<sub>2</sub> and PdRh Nanoparticles Supported at Regular and Defective MgO(001) Surfaces