CO, NO, and SO adsorption on Ni nanoclusters: a DFT investigation

Amorim, Rairisson V. de; Batista, Krys E. A.; Nagurniak, Glaucio Régis; Orenha, Renato Pereira; Parreira, Renato L. T.; Piotrowski, Maurício J.

doi:10.1039/d0dt00288g

Cited by 27 publications

(29 citation statements)

References 69 publications

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“…Furthermore, we have calculated the main XO gas-phase properties, which are the binding energies per atom of −5.76, −3.64, and −3.07 eV, equilibrium bond lengths of 1.14, 1.17, and 1.50 Å, and vibrational frequencies of 2122.20, 1918.40, and 1096.50 cm −1 for CO, NO, and SO, respectively. The agreement with previous DFT-PBE work is excellent, 19 while the largest deviations from the experimental results were 12.0% for the binding energies, 1.7% for the equilibrium bond lengths, and 3.7% for the vibrational modes. 85−89 The molecular adsorptions of CO, NO, and SO were performed on the lowest energy structures of Ir n (n = 2−7) nanoclusters since the most stable configuration for each size is one of the most probable structures to exist in an experimental situation.…”

Section: Resultssupporting

confidence: 83%

“…Among the manifold possible molecular environments to interact with Ir nanoclusters, the monoxide group composed of CO, NO, and SO are newsworthy. As previously studied, 19 the monoxide molecules have an appeal for their choice that lies in the environmental issue since carbon and nitrogen monoxides are air pollution gases, while sulfur monoxide is a poisonous contaminant associated with the acid rain formation, after the oxidation (SO 2 ) and water interaction. Thus, the investigation of the subnanometric Ir clusters in different XO (X = C, N, and S) chemical environments is important to elucidate the physical and chemical mechanisms for the energetic stabilization and to establish the chemical nature of interaction in dangerous molecular environments.…”

Section: Introductionmentioning

confidence: 99%

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Stability Changes in Iridium Nanoclusters via Monoxide Adsorption: A DFT Study within the van der Waals Corrections

et al. 2021

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Small iridium nanoclusters are prominent subnanometric systems for catalysis-related applications, mainly because of a large surface-to-volume ratio, noncoalescence feature, and tunable properties, which are completely influenced by the number of atoms, geometry, and molecular interaction with the chemical environment. Herein, we investigate the interaction between Ir n nanoclusters (n = 2− 7) and polluting molecules, CO, NO, and SO, using van der Waals D3 corrected density functional theory calculations. Starting from a representative structural set, we determine the growth pattern of the lowest energy unprotected Ir n nanoclusters, which is based on open structural motifs, and from the adsorption of a XO (X = C, N, and S) molecule, the preferred high-symmetric adsorption sites were determined, dominated by the onefold top site. For protected systems, 4XO/Ir 4 and 6XO/Ir 6 , we found a reduction in the total magnetic moment, while the equilibrium bonds of the nanoclusters expanded (contracted) due to mCO and mNO (mSO) adsorption, with exceptions for systems with large structural distortions (4SO/Ir 4 and 6NO/Ir 6 ). Meanwhile, the C−O and N−O (S−O) bond strength decreases (increases) following an increase (decrease) in the C− O and N−O (S−O) distances upon adsorption. We show, through energetic analysis, that for the different chemical environments, relative stability changes occur from the most stable unprotected nanoclusters, planar square (Ir 4 ), and prism (Ir 6 ) to higher energy isomers. The change in the stability order between the two competing protected systems is feasible if the balance between the interaction energy (additive term) and distortion energies (nonadditive terms) compensates for the relative total energies of the unprotected configurations. For all systems, the interaction energy is the main reason responsible for stability alterations, except for 4SO/Ir 4 , where the main contribution is from a small penalty due to Ir 4 distortions upon adsorption, and for 4NO/Ir 4 , where the energetic effects from the adsorption do not overcome the difference between the binding energies of the unprotected nanoclusters. Finally, from energy decomposition and Hirshfeld charge analysis, we find a predominant covalent nature of the physical contributions in mOX•••Ir n interactions with a cationic core (Ir n ) and an anionic shell (XO coverage).

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Section: Resultssupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Stability Changes in Iridium Nanoclusters via Monoxide Adsorption: A DFT Study within the van der Waals Corrections

et al. 2021

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“…Lei et al have reported that NO and NO 2 molecules get adsorbed with 2.47 and 3.73 eV adsorption energy, respectively, on La decorated phosphorene [53]. de Amorim et al have shown that CO, NO, and SO molecules get adsorbed on Ni 6 nanocluster with 2.18, 3.00, and 3.13 eV adsorption energy, respectively [54].…”

Section: Resultsmentioning

confidence: 99%

Titanium-benzene complex as a molecular oxide adsorbent: a first principles approach

et al. 2021

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CO, SO, NO, CO 2 , SO 2 , and NO 2 gas sensing properties of Ti-benzene (C 6 H 6 Ti) complex are studied with first principles calculations by analyzing change in structural parameters, electronic properties, and charge transfer. Adsorption of all six oxide molecules on C 6 H 6 Ti complex is found to be thermodynamically favorable at ambient conditions. The Gibbs free energy-corrected adsorption energy range for oxide molecules is found be 0.6-5.9 eV. The SO 2 transfers maximum charge to Ti metal, i.e., 0.36 (e − ) as compare to other oxides. The binding energy of Ti atom to benzene ring remains higher even after adsorption of oxide gas molecules. The higher values of HOMO-LUMO gap show that oxide-adsorbed complexes are chemically stable. The ADMP-MD simulations show that all oxide molecules remain adsorbed on Ti-benzene complex during the simulations for the temperature range 300-500 K. The Ti-benzene complex shows considerable gas sensing properties at ambient conditions.

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“…Regarding the EDA-NOCV, this technique has already been used in the context of metallic cluster studies, 55–57 and basically consists of decomposing the interaction energy, δ E int , of the two interacting fragments into physical meaningful terms according to:δ E int = δ E elst + δ E Pau + δ E orb + δ E disp ,where δ E elst stands for the quasi-classical electrostatic interaction between the unperturbed charge densities and nuclei of the geometrically deformed fragments; the Pauli δ E Pau term contains the destabilizing interactions between occupied orbitals of the fragments, being responsible for the steric repulsion; the δ E orb term accounts for the orbital interactions between the occupied and unoccupied orbitals of interacting fragments (charge transfer, i.e. , donor–acceptor interactions between the occupied orbitals in one fragment with the empty orbitals of another moiety) and on the same fragment (polarization, i.e.…”

Section: Methodsmentioning

confidence: 99%

The effect of different energy portions on the 2D/3D stability swapping for 13-atom metal clusters

Guedes-Sobrinho

Orenha

Parreira

et al. 2022

Phys. Chem. Chem. Phys.

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CO, NO, and SO adsorption on Ni nanoclusters: a DFT investigation

Abstract: From our ab initio investigation, we have improved the understanding of the interaction between Nickel nanoclusters and diatomic molecules, such as CO, NO, and SO, to provide insights into real subnano catalysts.

Cited by 27 publications

References 69 publications

Stability Changes in Iridium Nanoclusters via Monoxide Adsorption: A DFT Study within the van der Waals Corrections

Stability Changes in Iridium Nanoclusters via Monoxide Adsorption: A DFT Study within the van der Waals Corrections

Titanium-benzene complex as a molecular oxide adsorbent: a first principles approach

The effect of different energy portions on the 2D/3D stability swapping for 13-atom metal clusters

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