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. 2024 Apr 26;9(18):20467-20476.
doi: 10.1021/acsomega.4c01557. eCollection 2024 May 7.

Unraveling Hydrogen Adsorption on Transition Metal-Doped [Mo3S13]2- Clusters: Insights from Density Functional Theory Calculations

Thu Thi Phung  1   2 , Nguyen Thi Huyen  1 , Nguyen Thi Giang  1 , Nguyen Minh Thu  1 , Nguyen Thanh Son  1 , Nguyen Hoang Tung  1 , Ngo Thi Lan  1   3 , Son Tung Ngo  4   5 , Nguyen Thi Mai  1 , Nguyen Thanh Tung  1   6
Affiliations

Unraveling Hydrogen Adsorption on Transition Metal-Doped [Mo3S13]2- Clusters: Insights from Density Functional Theory Calculations

Thu Thi Phung et al. ACS Omega. .

Abstract

Molecular and dissociative hydrogen adsorption of transition metal (TM)-doped [Mo3S13]2- atomic clusters were investigated using density functional theory calculations. The introduced TM dopants form stable bonds with S atoms, preserving the geometric structure. The S-TM-S bridging bond emerges as the most stable configuration. The preferred adsorption sites were found to be influenced by various factors, such as the relative electronegativity, coordination number, and charge of the TM atom. Notably, the presence of these TM atoms remarkably improved the hydrogen adsorption activity. The dissociation of a single hydrogen molecule on TM[Mo3S13]2- clusters (TM = Sc, Cr, Mn, Fe, Co, and Ni) is thermodynamically and kinetically favorable compared to their bare counterparts. The extent of favorability monotonically depends on the TM impurity, with a maximum activation barrier energy ranging from 0.62 to 1.58 eV, lower than that of the bare cluster (1.69 eV). Findings provide insights for experimental research on hydrogen adsorption using TM-doped molybdenum sulfide nanoclusters, with potential applications in the field of hydrogen energy.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Lowest-energy configurations of bare [Mo3S13]2– and TM[Mo3S13]2– (TM = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) clusters. Turquoise, yellow, and red spheres denote Mo, S, and H, respectively. Light gray, gray, dark gray, pink, violet, slate blue, blue, and royal blue spheres represent Sc, Ti, V, Cr, Mn, Fe, Co, and Ni, respectively.
Figure 2
Figure 2
Lowest-energy configurations of bare [Mo3S13]2––H2 and TM[Mo3S13]2––H2 (TM = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) clusters. Turquoise, yellow, and red spheres denote Mo, S, and H, respectively. Light gray, gray, dark gray, pink, violet, slate blue, blue, and royal blue spheres represent Sc, Ti, V, Cr, Mn, Fe, Co, and Ni, respectively.
Figure 3
Figure 3
Lowest-energy configurations of bare [Mo3S13]2––2H and TM[Mo3S13]2––2H (TM = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) clusters. Turquoise, yellow, and red spheres denote Mo, S, and H, respectively. Light gray, gray, dark gray, pink, violet, slate blue, blue, and royal blue spheres represent Sc, Ti, V, Cr, Mn, Fe, Co, and Ni, respectively.
Figure 4
Figure 4
Calculated reaction pathways and relative energies (eV) for the molecular and dissociative adsorption of H2 on bare- (singlet) and Sc-doped (quartet) clusters. Intermediates and TSs are denoted as Ii and TSi.
Figure 5
Figure 5
Calculated reaction pathways and relative energies (eV) for the molecular and dissociative adsorption of H2 on Ti- (singlet) and Mn-doped (sextet) clusters. Intermediates and TSs are denoted as Ii and TSi.
Figure 6
Figure 6
Calculated reaction pathways and relative energies (eV) for the molecular and dissociative adsorption of H2 on Cr- (quintet) and Fe-doped (quintet) cluster. Intermediates and TSs are denoted as Ii and TSi.
See this image and copyright information in PMC

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