Water dissociation and association on mirror twin boundaries in two-dimensional MoSe2: insights from density functional theory calculations

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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en

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10

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Nanoscale Advances, Volume 3, issue 24, pp. 6992-7001

Abstract

The adsorption and dissociation of water molecules on two-dimensional transition metal dichalcogenides (TMDs) is expected to be dominated by point defects, such as vacancies, and edges. At the same time, the role of grain boundaries, and particularly, mirror twinboundaries (MTBs), whose concentration in TMDs can be quite high, is not fully understood. Using density functional theory calculations, we investigate the interaction of water, hydroxyl groups, as well as oxygen and hydrogen molecules with MoSe2 monolayers when MTBs of various types are present. We show that the adsorption of all species on MTBs is energetically favorable as compared to that on the basal plane of pristine MoSe2, but the interaction with Se vacancies is stronger. We further assess the energetics of various surface chemical reactions involving oxygen and hydrogen atoms. Our results indicate that water dissociation on the basal plane should be dominated by vacancies even when MTBs are present, but they facilitate water clustering through hydroxyl groups at MTBs, which can anchor water molecules and give rise to the decoration of MTBs with water clusters. Also, the presence of MTBs affects oxygen reduction reaction (ORR) on the MoSe2 monolayer. Unlike Se vacancies which inhibit ORR due to a high overpotential, it is found that the ORR process on MTBs is more efficient, indicating their important role in the catalytic activity of MoSe2 monolayer and likely other TMDs.

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Joseph, T, Ghorbani-Asl, M, Batzill, M & Krasheninnikov, A 2021, 'Water dissociation and association on mirror twin boundaries in two-dimensional MoSe2 : insights from density functional theory calculations', Nanoscale Advances, vol. 3, no. 24, pp. 6992-7001. https://doi.org/10.1039/d1na00429h