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Link to original content: http://pubmed.ncbi.nlm.nih.gov/38986139/
Acetylene and Ethylene Adsorption during Floating Fe Catalyst Formation at the Onset of Carbon Nanotube Growth and the Effect of Sulfur Poisoning: a DFT Study - PubMed Skip to main page content
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. 2024 Jul 22;63(29):13624-13635.
doi: 10.1021/acs.inorgchem.4c01830. Epub 2024 Jul 10.

Acetylene and Ethylene Adsorption during Floating Fe Catalyst Formation at the Onset of Carbon Nanotube Growth and the Effect of Sulfur Poisoning: a DFT Study

Balázs Orbán  1 , Tibor Höltzl  1   2   3
Affiliations

Acetylene and Ethylene Adsorption during Floating Fe Catalyst Formation at the Onset of Carbon Nanotube Growth and the Effect of Sulfur Poisoning: a DFT Study

Balázs Orbán et al. Inorg Chem. .

Abstract

Here, we investigated the adsorption of acetylene and ethylene on iron clusters and nanoparticles, which is a crucial aspect in the nascent phase of carbon nanotube growth by floating catalyst chemical vapor deposition (FCCVD). The effect of sulfur on adsorption was also studied due to its indispensable role in the process and its commonly known impact on metal catalyst poisoning. We performed systematic density functional theory (DFT) computations, considering numerous adsorption configurations and iron particles of various sizes (Fen, n = 3-10, 13, 55). We found that acetylene binds significantly more strongly than ethylene and prefers different adsorption sites. The presence of sulfur decreased the adsorption strength only in the immediate proximity of the adsorbate, suggesting that the effect of sulfur is mainly of steric origin while electronic effects play only a minor role. Higher sulfur coverage of the catalyst surface significantly weakened the binding of acetylene or ethylene. To further investigate this interaction, Bader's atoms in molecules (AIM) analysis and charge density difference (CDD) were used, which showed electron transfer from iron clusters or nanoparticles to the adsorbate molecules. The charge transfer exhibited a decreasing trend as sulfur coverage increased. These results can also contribute to the understanding of other iron-based catalytic processes involving hydrocarbons and sulfur, such as the Fischer-Tropsch synthesis.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Schematic Representation of CNT Growth in the FCCVD Method
Scheme 2
Scheme 2. Binding Modes of Ethylene and Acetylene on Transition Metal Surfaces or Nanoparticles
M represents a transition metal atom.
Figure 1
Figure 1
Optimized structures of Fen (n = 3–10,13,55) clusters. mFe is the magnetic moment per Fe atom, and daverage is the average bond length in each system.
Figure 2
Figure 2
Most stable acetylene and ethylene adsorption sites on Fen (n = 3–10, 13, 55). The calculated binding energies (Eb) are given in kJ/mol.
Figure 3
Figure 3
Optimized structures of Fe13S and Fe55S.
Figure 4
Figure 4
Adsorption of acetylene and ethylene on Fe13S and Fe55S with different sulfur–adsorbate molecule configurations. The calculated binding energies (Eb) are shown in kJ/mol.
Figure 5
Figure 5
Acetylene and ethylene adsorption on Fe13S7, Fe55S5 and Fe13S20. The calculated binding energies (Eb) are shown in kJ/mol.
Figure 6
Figure 6
Energy decomposition, Bader, and charge density difference (CDD) analysis of acetylene and ethylene adsorption on Fe5, Fe13, Fe13S, Fe13S7, and Fe55. The calculated binding (Eb), interaction (Eint), and deformation (Edef) energies are shown in kJ/mol, while ΔQFe/FeS, ΔQC, and ΔQH are the total Bader charges for each atom type.
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