Underpotential deposition on free nanoparticles: Its meaning and measurement

The meaning of underpotential shift is discussed for free nanoparticles, where a redox couple is used to set potential control on them. Atomistic Monte Carlo simulations are performed to study their decoration in the submonolayer regime. The resulting configurations are used to simulate their plasmon spectra by means of a state-of-the art quantum mechanical atomistic model.

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► The concept of underpotential (upd) phenomenon is extended to nanoparticles (NPs).
► Computer simulations are performed for the growth of core@shell NPs.
► The measurement of upd through surface plasmon resonances is analyzed.
► The possibility of selective decoration of NP facets through upd is demonstrated.