jp8b08549_si_001.pdf (14.69 MB)
Kinetics-Based Computational Catalyst Design Strategy for the Oxygen Evolution Reaction on Transition-Metal Oxide Surfaces
journal contribution
posted on 2018-11-01, 00:00 authored by Craig P. Plaisance, Simeon D. Beinlich, Karsten ReuterDensity functional
theory was used to examine the oxygen evolution
reaction on a large number of active sites formed by doping three
different surfaces of Co3O4 with various 3d
transition-metal atoms. By combining the scaling and Brønsted–Evans–Polanyi
(BEP) relationships that are determined for these sites, it is shown
that the activity of a site is controlled by the redox potential for
oxidation of the site. On the basis of this, a kinetics-based design
strategy is presented for identifying the optimal active site at a
given electrode potential. This design strategy is shown to be valid
regardless of whether the rate-limiting water addition step occurs
electrochemically or nonelectrochemically, as long as certain conditions
are met. Another finding is that the BEP relations are sensitive to
the structure of the active site, with sites reacting through μ3-oxo species having the most favorable relations. Finally,
the kinetics-based design strategy is compared with the commonly used
thermodynamics-based design strategy, and it is shown that the former
is able to identify a site with equal or greater activity than the
latter at the same computational cost.
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Transition-Metal Oxide Surfaces Densityoxygen evolution reactionsitetransition-metal atomsμ 3design strategyOxygen Evolution ReactionBEP relationsthermodynamics-based design strategyrate-limiting water addition stepoxo speciesCo 3 O 4Br ønstedkinetics-based design strategyKinetics-Based Computational Catalyst Design Strategy
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