The CO chemisorption on some active sites of Pd clusters: A DFT study

Bertin, V.; Agacino, Esther; López-Rendón, Roberto; Poulain, E.

doi:10.1016/j.theochem.2006.04.026

Cited by 31 publications

(24 citation statements)

References 20 publications

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“…Only the data for the ground C 2v state are shown in Table 3. This result is consistent with the structural study conducted by the group of V. Bertin [14] and the group of P. Nava. [15] Comparing to PdCO, there is greater charge transfer from 4d orbitals to the π* orbitals of the CO for the Pd 2 CO complex.…”

Section: Resultssupporting

confidence: 93%

“…[8][9][10][11][12] Recently, palladium clusters with larger nuclearity were also studied by molecular dynamics. [13] Interactions of ligands with the metal core have also been the subject of a series of works which include, among others, interactions with CO, [14,15] NO, [16] S and Cl, [17] O 2 [18] or H and CH x . [19] In this work, we intend to push further the investigation of these species by addressing in greater detail their electronic structure.…”

Section: Introductionmentioning

confidence: 99%

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DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

Zanti

Peeters

2009

Eur J Inorg Chem

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This paper presents a theoretical study of palladium clusters Pd n of low nuclearity, ranging from 1 to 9, completed by their interactions with a carbonyl ligand (Pd n CO). The simulations were performed at the DFT (B3LYP-Lanl2DZ) level. Small palladium clusters are deltahedral structures characterized by a triplet ground state (Pd 2 to Pd 7 ) or a quintet ground state for larger nuclearities (Pd 8 and Pd 9 ). Various electronic states relatively close in energy are present. These states have close geometries but differ by their electron density distribution. A significant electronic population of the 5s orbital is needed to explain the existence and cohesion of palladium-palladium bonds. These latter are formed by the combination of sd hybrid orbitals and get stronger as the 5s character increases. The relative stability of palladium clusters increases with their nuclearity and the study of fragmentation reactions

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Section: Resultssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

Zanti

Peeters

2009

Eur J Inorg Chem

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“…Binding energy of CO in the lowest energy Pd 4 CO complex is found to be less, while CÀ ÀO bond length agrees well with the earlier results. 43,44 CÀ ÀO stretching frequency in this complex is found to be less than the earlier observations. 44,42 For cationic complexes, structure with bridge adsorption site for CO (Pd 4 CO 1 in Figure 1) lies 0.15 eV higher in energy than the most stable structure, Pd 4 CO 1*…”

Section: Adsorption Of Co On Pd 4 Clusterscontrasting

confidence: 77%

Adsorption of CO on oxygen preadsorbed neutral and charged gas phase Pd₄ clusters: A density functional study

Kalita¹,

Deka²

2010

J Comput Chem

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We present the results of a density functional calculation on adsorption of O(2), CO, and their coadsorption at various sites of neutral, cationic, and anionic Pd(4) clusters. For all the clusters, the dissociative adsorption of oxygen sitting on Pd bridge sites is found to be preferable. Both O(2) and CO binding energies are found to be higher for the anionic Pd(4) cluster followed by cationic and neutral cluster. However, binding energies of O(2) or CO in the coadsorption complexes follow the trend: anionic > neutral > cationic.

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“…Previously, we have employed the B3LYP functional to study the CO chemisorption on Pd clusters [24]. In 2007, Paier et al [25] published the article: BWhy does the B3LYP hybrid functional fail for metals?^.…”

Section: Computational Detailsmentioning

confidence: 99%

The CO oxidation mechanism on small Pd clusters. A theoretical study

et al. 2015

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CO is a pollutant that is removed by oxidation using Pd, Pt or Rh as catalysts in the exhaust pipes of vehicles. Here, a quantum chemistry study on the CO + O2 reaction catalyzed by small Pdn clusters (n ≤ 5) using the PBE/TZ2P/ZORA method is performed. The limiting step in this reaction at low temperature and coverage is the O2 dissociation. Pdn clusters catalyze the O=O bond breaking, reducing the energy barrier from 119 kcal mol(-1) without catalyst to ∼35 kcal mol(-1). The charge transfer from Pd to the O2,ad antibonding orbital weakens, and finally breaks the O─O bond. The CO oxidation takes place by the Eley-Rideal (ER) mechanism or the Langmuir-Hinshelwood (LH) mechanism. The ER mechanism presents an energy barrier of 4.10-7.05 kcal mol(-1) and the formed CO2 is released after the reaction. The LH mechanism also shows barrier energies to produce CO2 (7-15 kcal mol(-1)) but it remains adsorbed on Pd clusters. An additional energy (7-25 kcal mol(-1)) is necessary to desorb CO2 and release the metal site. The triplet multiplicity is the ground states of studied Pdn clusters, with the following order of stability: triplet > singlet > quintet state. Graphical Abstract CO oxidation mechanism on small Pd clusters.

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The CO chemisorption on some active sites of Pd clusters: A DFT study

Cited by 31 publications

References 20 publications

DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

Adsorption of CO on oxygen preadsorbed neutral and charged gas phase Pd₄ clusters: A density functional study

The CO oxidation mechanism on small Pd clusters. A theoretical study

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The CO chemisorption on some active sites of Pd clusters: A DFT study

Cited by 31 publications

References 20 publications

DFT Study of Small Palladium Clusters Pdn and Their Interaction with a CO Ligand (n = 1–9)

DFT Study of Small Palladium Clusters Pdn and Their Interaction with a CO Ligand (n = 1–9)

Adsorption of CO on oxygen preadsorbed neutral and charged gas phase Pd4 clusters: A density functional study

The CO oxidation mechanism on small Pd clusters. A theoretical study

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DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

DFT Study of Small Palladium Clusters Pd_n and Their Interaction with a CO Ligand (n = 1–9)

Adsorption of CO on oxygen preadsorbed neutral and charged gas phase Pd₄ clusters: A density functional study