Cu(111) single crystal electrodes: Modifying interfacial properties to tailor electrocatalysis

Tailoring electrocatalyst materials to the specific requirements of a certain reaction and to optimize activity or enhance selectivity is a key tactic for the development of low-temperature fuel and electrolyzer cells for clean energy production. Here, we demonstrate the modification of Cu(111) electrodes with different sub-monolayer coverages of foreign metals (Cd) and metal hydroxides (Co(OH) 2 and Ni(OH) 2 ) for application in the hydrogen evolution reaction (HER) in alkaline media. In situ electrochemical scanning tunneling microscopy (EC-STM) reveals that these modifications have a significant influence on the morphology and structure of the Cu(111) surface with its characteristics depending on both the nature and the amount of the adsorbed metal(hydroxide). Ni(OH) 2 and Co(OH) 2 on Cu(111) lead to a significant enhancement of the electrocatalytic activity towards the HER in alkaline electrolyte, whereas a decrease in activity is found for Cd modified Cu(111). These trends can be rationalized by considering the strength of the interfacial electric field and its influence on the specific interactions of the electrode with the water ad-layer close to the surface, as determined by laser-induced temperature jump measurements. This comparative study therefore provides valuable information on the structure-activity relation as well as insights on the interfacial characteristics of different bimetallic Cu electrocatalysts. (c) 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license ( http://creativecommons.org/licenses/by/4.0/ )

Automated summary

Modifying Cu(111) electrodes with different foreign metals or metal hydroxides can significantly influence the electrocatalytic activity for the hydrogen evolution reaction, with Ni(OH)2 and Co(OH)2 enhancements and Cd decreases observed.