Structure, reactivity and electronic properties of Mn doped clusters

Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit

doi:10.1016/j.physb.2013.03.027

Cited by 8 publications

(1 citation statement)

References 21 publications

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“…In particular, for each vertex Ni atom of Ni 13 , possessing the coordinative unsaturated site, is the predominant active center. The γ-Al 2 O 3 (110) , offers a template, which is modeled using a supercell with two dimensions of 11.70 × 11.70 × 22.18 Å 3 and 8.43 × 8.11 × 20.18 Å 3 , and then the Zr 2 Ni 11 , and ZrNi 3 NPs are deposited on their templates, respectively. The configurations are assigned to (a) Zr 2 Ni 11 , (b) Zr 2 Ni 11 /Al 2 O 3 , and (c) ZrNi 3 /Al 2 O 3 , as shown in Figure .…”

Section: Computational Detailsmentioning

confidence: 99%

Unraveling the Role of the d-Electron Reservoir of ZrNi₃/Al₂O₃ for C–O Breaking during CO Methanation: Zr-Induced Active Sites Make the Difference

Zhi

Yang

2023

J. Phys. Chem. C

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According to density functional theory results, ZrNi 3 / Al 2 O 3 exhibits a higher activity of CO methanation with a decreased E a of the C−O bond breaking compared to Zr 2 Ni 11 and Zr 2 Ni 11 /Al 2 O 3 . This phenomenon is attributed to the presence of active, lowcoordinated sites of the Zr-promoter and the large electronic perturbations in contact with the Al 2 O 3 support. The calculations demonstrate that the Zr-promoting effect on C−O breaking is due to the synergy between Zr, Ni, and Al 2 O 3 , leading to a shift of ε d of ZrNi 3 / Al 2 O 3 . This promoting effect is able to reduce the electrical band gap of the CO dissociation by creating a new energy state between the d-state of ZrNi 3 /Al 2 O 3 and the p-state of CO. Even more, this promoting effect tunes C 2p and O 2p to higher energy, sufficient to produce the more 2π*antibonding states, and thus, enough to weaken further the C−O bond resulting in a more reactive CO. More importantly, ZrNi 3 / Al 2 O 3 activates CO efficiently, prevents the production of CH 3 OH, and via the direct C−O breaking pathway generates CH 4 .

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