Electrodeposition of metal adlayers on semiconductor metal chalcogenides (CdSe, CdS, PbTe, PbSe, PbS, Bi2Te3) is reviewed. Cathodic underpotential deposition of metal adlayer on metal chalcogenide is the electrochemically irreversible surface limited reaction. The irreversibility of the upd increases in the row from tellurides to selenides and further to sulfides. The underpotential shift on chalcogenide nanoparticles increases with particle size. Metal upd on chalcogenides is applied as a means of measurement of electroactive surface area of chalcogenide electrodes. The method is especially advantageous for multicomponent systems with other component not supporting upd, such as CdSe-TiO2, CdSe-ZnO. Differences of voltammetric profiles of Pb upd on Bi2Te3 and Te are applied for detection of Bi2Te3 surface contamination by elemental tellurium. The further tasks in the electrochemistry of metal adlayers are their incorporation as interlayers in layered chalcogenides and electrodeposition of superlattices.

This is a pre-print of an article published in J. Solid State Electrochem.. The final authenticated version is available online at: https://doi.org/10.1007/s10008-020-04681-4