Theoretical study of the adsorption of carbon monoxide on small copper clusters

Padilla-Campos, Luis

doi:10.1016/j.theochem.2007.10.027

Cited by 36 publications

(24 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Finally, in both systems (Li m Cu n O 2 and Cu n O 2 ), the molecular oxygen adsorption produces systems that tend to preserve a high symmetry of the adsorption system. This latter behavior has also been found for the adsorption of oxygen, atomic and molecular, and CO on copper clusters as recently reported 17, 18, 32. Therefore, the tendency is toward maintaining a high symmetry of the adsorption system.…”

Section: Resultssupporting

confidence: 80%

Theoretical investigation of the adsorption of oxygen on small bimetallic Li_mCu_n (m, n ≤ 4) clusters

Padilla-Campos

2009

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

ABSTRACT:A theoretical study of the adsorption of molecular oxygen on small bimetallic Li m Cu n (m, n Յ 4) clusters was carried out using density functional methods, and it was compared with the adsorption of O 2 on copper (Cu n , n Յ 8) clusters. The study of O 2 -Li m Cu n system is important to understand the promotion effects of the alkali atoms on the copper surface participating in the catalytic processes. Adsorption energies ranging from 7.9 to 51 kcal/mol were found, which represented values over 30% to those calculated for the adsorption of O 2 on copper clusters in a previous study. Thus, the reactivity of molecular oxygen on bimetallic clusters is more favorable with high tendency being in favor of the dissociation of the O 2 molecule.

show abstract

Section: Resultssupporting

confidence: 80%

Theoretical investigation of the adsorption of oxygen on small bimetallic Li_mCu_n (m, n ≤ 4) clusters

Padilla-Campos

2009

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…The interaction of CO and O 2 with Cu n clusters with n ≤ 10 atoms and the dissociative chemisorption of H 2 on Cu n clusters of up to 15 atoms have been explored in detail, and a higher reactivity of copper clusters with an odd number of atoms has been reported with few exceptions. [30][31][32][33][34][35][36] As regards mechanistic studies, only the dissociation of H 2 O on Cu 7 37 and the mechanism of CO oxidation on Cu 6 and Cu 7 clusters 38 have been reported in the literature.We present now a systematic theoretical study of O 2 adsorption and dissociation on Cu n clusters with n=3-8, 13, and 38 atoms, this last model being considered here the size limit between clusters and nanoparticles. Different modes of adsorption of molecular O 2 have been considered for each atomicity of the copper clusters, and the transition states for dissociation of the O-O bond have been calculated with the objective of finding a trend with particle size in the reactivity of copper clusters.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

2015

View full text Add to dashboard Cite

The adsorption and dissociation of molecular O 2 on copper clusters of varying size and morphology (Cu n with n=3-8, 13, and 38 atoms) has been systematically investigated using several DFT approaches. Different modes of adsorption of molecular O 2 are found for each atomicity of the copper clusters, with their relative stability depending on the cluster morphology: bridge conformations are stabilized on planar clusters, while hollow h-100 and h-111 modes are preferentially formed on 3D clusters. O 2 adsorption energies correlate with the HOMO energy of the isolated copper clusters, but not with their atomicity. On the other hand, the degree of activation of the O-O bond, and therefore the activation energy barrier necessary to break it, depends on the charge transferred to the π* MO of O 2 , which in turn is determined by the mode of adsorption of O 2 on the metal. Cluster morphology appears then as the key factor determining the catalytic activity of copper, since the most activating h-111 and h-100adsorption modes leading to lower barriers are preferentially stabilized on 3D clusters, no matter their size.All computational levels considered, including periodic and molecular calculations, lead to similar trends and conclusions.properties of small copper clusters, in some cases combined with photoelectron spectroscopy measurements, can be found in the literature. [25][26][27][28][29] The reactivity of copper clusters, and its evolution with the number of atoms in the cluster, has been less investigated. The interaction of CO and O 2 with Cu n clusters with n ≤ 10 atoms and the dissociative chemisorption of H 2 on Cu n clusters of up to 15 atoms have been explored in detail, and a higher reactivity of copper clusters with an odd number of atoms has been reported with few exceptions. [30][31][32][33][34][35][36] As regards mechanistic studies, only the dissociation of H 2 O on Cu 7 37 and the mechanism of CO oxidation on Cu 6 and Cu 7 clusters 38 have been reported in the literature.We present now a systematic theoretical study of O 2 adsorption and dissociation on Cu n clusters with n=3-8, 13, and 38 atoms, this last model being considered here the size limit between clusters and nanoparticles. Different modes of adsorption of molecular O 2 have been considered for each atomicity of the copper clusters, and the transition states for dissociation of the O-O bond have been calculated with the objective of finding a trend with particle size in the reactivity of copper clusters.There is, however, a methodological issue in the systematic study of metal clusters of increasing size, which is mainly related to the scaling of the computational cost with the number of electrons in the system. Density functional theory (DFT) 39, 40 based methods are usually chosen because they provide reasonable accuracy at a relatively moderate computational cost. However, the cost of a DFT calculation based on atom-centered Gaussian orbitals scales with N 3 , being N the number of functions in the basis set. [41][42][43] This means that e...

show abstract

“…Several studies on the interaction of nanotubes, boron nitride 3 and other metallic clusters with NO and CO have been reported in the past, theoretically [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] and experimentally. 24 However, the interaction of (BN) n clusters have not been studied yet.…”

Section: Introductionmentioning

confidence: 99%

DFT STUDY OFCOANDNOADSORPTION ON BORON NITRIDE (BN)_{n = 3 - 5}NANOCLUSTERS

2015

View full text Add to dashboard Cite

Interaction of CO and NO molecules by di®erent orientations on (BN) n¼3À5 clusters have been studied at the B3LYP/6-311þG* level of theory. Total electronic energies have been corrected for geometrical counterpoise (gCP) and dispersion (D3) energies at the B3LYP/6-31G* level. Formation of a new sigma bond between the gas and (BN) 3 cluster, atom in molecules (AIM) results, density of states spectrums (DOS), molecular electrostatic potential (MEP) surfaces, and visualization of wave function of molecular orbitals in the nearest bonding regions to the Fermi level have con¯rmed that adsorption of CO by carbon end atom, and NO by nitrogen end atom is covalent in nature, so that the charge transfer is occurred from gas molecule to the cluster.

show abstract

Theoretical study of the adsorption of carbon monoxide on small copper clusters

Cited by 36 publications

References 34 publications

Theoretical investigation of the adsorption of oxygen on small bimetallic Li_mCu_n (m, n ≤ 4) clusters

Theoretical investigation of the adsorption of oxygen on small bimetallic Li_mCu_n (m, n ≤ 4) clusters

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

DFT STUDY OFCOANDNOADSORPTION ON BORON NITRIDE (BN)_{n = 3 - 5}NANOCLUSTERS

Contact Info

Product

Resources

About

Theoretical study of the adsorption of carbon monoxide on small copper clusters

Cited by 36 publications

References 34 publications

Theoretical investigation of the adsorption of oxygen on small bimetallic LimCun (m, n ≤ 4) clusters

Theoretical investigation of the adsorption of oxygen on small bimetallic LimCun (m, n ≤ 4) clusters

Trends in the Reactivity of Molecular O2 with Copper Clusters: Influence of Size and Shape

DFT STUDY OFCOANDNOADSORPTION ON BORON NITRIDE (BN)n = 3 - 5NANOCLUSTERS

Contact Info

Product

Resources

About

Theoretical investigation of the adsorption of oxygen on small bimetallic Li_mCu_n (m, n ≤ 4) clusters

Theoretical investigation of the adsorption of oxygen on small bimetallic Li_mCu_n (m, n ≤ 4) clusters

Trends in the Reactivity of Molecular O₂ with Copper Clusters: Influence of Size and Shape

DFT STUDY OFCOANDNOADSORPTION ON BORON NITRIDE (BN)_{n = 3 - 5}NANOCLUSTERS