Abstract
The advances in material science have led to the development of novel and various materials as nanoparticles or thin films. Underpotential deposition (upd) of transition metals appears to be a very sensitive method for probing the surfaces of noble metals, which is a parameter that has an important effect on the activity in heterogeneous catalysis. Underpotential deposition as a surface characterization tool permits researchers to precisely determine the crystallographic orientations of nanoparticles or the real surface area of various surfaces. Among all the work dealing with upd, this review focuses specifically on the main upd systems used to probe surfaces of noble metals in electrocatalysis, from poly‒ and single-crystalline surfaces to nanoparticles. Cuupd is reported as a tool to determine the active surface area of gold‒ and platinum‒based bimetallic electrode materials. Pbupd is the most used system to assess the crystallographic orientations on nanoparticles’ surface. In the case of platinum, Bi and Ge adsorptions are singled out for probing (1 1 1) and (1 0 0) facets, respectively.
Highlights
Surface of materials is a key parameter in heterogeneous catalysis
Referring the current density to the geometric surface area does not consider the surface structure of the material, the active sites at the surface of a material depend on its structure, the characterization of material surface in electrocatalysis becomes an important step in understanding the reactions that occur and evaluating their activity
Pbupd appears to be an efficient tool to characterize the surface of gold nanoparticles (AuNPs)
Summary
Surface of materials is a key parameter in heterogeneous catalysis. In electrocatalysis, it is the reaction site where the exchange of electrons occurs, thereby the structure of the materials or any roughness affect their electrochemical response. Several electrochemical methods are used for characterizing the material surface. The upd is sensitive to local order, contrary to electron diffraction methods such as Low Energy Electron. The upd can be carried out on polycrystalline surfaces, single-crystals, and recently nanoparticles. The latter have different shapes and sizes that involve different surface structures leading to a variety of activities observed in heterogeneous catalysis and in electrocatalysis.
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