Electronic Spillover from a Metallic Nanoparticle: Can Simple Electrochemical Electron Transfer Processes Be Catalyzed by Electronic Coupling of a Molecular Scale Gold Nanoparticle Simultaneously to the Redox Molecule and the Electrode?

Electrochemical electron transfer (ET) of transition metal complexes or redox metalloproteins can be catalyzed by more than an order of magnitude by molecular scale metallic nanoparticles (NPs), often rationalized by concentration enhancement of the redox molecules in the interfacial region, but collective electronic AuNP array effects have also been forwarded. Using DFT combined with molecular electrochemical ET theory we explore here whether a single molecular scale Au nanocluster (AuC) between a Au (111) surface and the molecular redox probe ferrocene/ferricinium (Fc/Fc+) can trigger an ET rate increase. Computational challenges limit us to AunCs (n up to 147), which are smaller than most electrocatalytic AuCs studied experimentally. AuC-coating thiols are addressed both as adsorption of two S atoms at the structural Au55 bridge sites and as superexchange of variable-size AuCs via a single six-carbon alkanethiyl bridge. Our results are guiding, but enable comparing many AuC surface details (apex, ridge, face, direct vs superexchange ET) with a planar Au(111) surface. The rate-determining electronic transmission coefficients for ET between Fc/Fc+ and AuC are highly sensitive to subtle AuC electronic features. The transmission coefficients mostly compete poorly with direct Fc/Fc+ ET at the Au(111) surface, but Fc/Fc+ 100 face-bound on Au79 and Au147 and ridge bound on Au19 leads to a 2- or 3-fold rate enhancement, in different distance ranges. Single AuCs can thus indeed cause rate enhancement of simple electrochemical ET, but additional, possibly collective AuNC effects, as well as larger clusters and more complete coating layers, also need to be considered.