Metal deposition via electroless surface limited redox replacement

• A new metal deposition strategy, ESLRR, is realized without the use of external power.
• A UPD sacrificial layer for the SLRR event is generated in a galvanic cell configuration.
• Ag deposition on Au by ESLRR proceeds in quasi-2D growth mode for up to 50 deposition cycles.
• The ESLRR approach can be extended to industrially relevant Pt, Pd, Au, & Cu coatings.

The development of electroless SLRR (ESLRR) utilizing a galvanic cell configuration is demonstrated at a proof-of concept level by the deposition of epitaxial Ag layers on Au. ESLRR is realized via the connection and subsequent disconnection of an Au working electrode (WE) to a Pb “executive” electrode (EE). The connection leads to the underpotential deposition of a Pb monolayer at the WE driven by the stripping of an equivalent amount of Pb from the EE. The disconnection then enables the galvanic displacement of the Pb monolayer by Ag. Electrochemical and in-situ STM characterizations of deposited Ag films show high-quality 2D-growth with no roughness development for up to 50 ESLRR cycles. This approach can be extended to a variety of metal-substrate pairs widely applicable in electrocatalysis and energy applications.

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