Oxygen Evolution Reaction on Nitrogen-Doped Defective Carbon Nanotubes and Graphene

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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en

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12

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Journal of Physical Chemistry C, Volume 122, issue 45, pp. 25882-25892

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The realization of a hydrogen economy would be facilitated by the discovery of a water-splitting electrocatalyst that is efficient, stable under operating conditions, and composed of earth-abundant elements. Density functional theory simulations within a simple thermodynamic model of the more difficult half-reaction, the anodic oxygen evolution reaction (OER), with a single-walled carbon nanotube as a model catalyst, show that the presence of 0.3-1% nitrogen reduces the required OER overpotential significantly compared to the pristine nanotube. We performed an extensive exploration of systems and active sites with various nitrogen functionalities (graphitic, pyridinic, or pyrrolic) obtained by introducing nitrogen and simple lattice defects (atomic substitutions, vacancies, or Stone-Wales rotations). A number of nitrogen functionalities (graphitic, oxidized pyridinic, and Stone-Wales pyrrolic nitrogen systems) yielded similar low overpotentials near the top of the OER volcano predicted by the scaling relation, which was seen to be closely observed by these systems. The OER mechanism considered was the four-step single-site water nucleophilic attack mechanism. In the active systems, the second or third step, the formation of attached oxo or peroxo moieties, was the potential-determining step of the reaction. The nanotube radius and chirality effects were examined by considering OER in the limit of large radius by studying the analogous graphene-based model systems. They exhibited trends similar to those of the nanotube-based systems but often with reduced reactivity due to weaker attachment of the OER intermediate moieties. © 2018 American Chemical Society.

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Murdachaew, G & Laasonen, K 2018, 'Oxygen Evolution Reaction on Nitrogen-Doped Defective Carbon Nanotubes and Graphene', Journal of Physical Chemistry C, vol. 122, no. 45, pp. 25882-25892. https://doi.org/10.1021/acs.jpcc.8b08519