Preparation of complex model electrocatalysts in ultra-high vacuum and transfer into the electrolyte for electrochemical IR spectroscopy and other techniques

Abstract

Model studies at complex, yet well-defined electrodes can provide a better understanding of electrocatalytic reactions. New experimental devices are required to prepare such model electrocatalysts with atomic-level control. In this work, we discuss the design of a new setup, which enables the preparation of well-defined electrocatalysts in ultra-high vacuum (UHV) using the full portfolio of surface science techniques. The setup allows for direct transfer of samples from UHV and the immersion into the electrolyte without contact to air. As a special feature, the single crystal sample is transferred without any sample holder, which makes the system easily compatible with most electrochemical <i>in situ</i> methods, specifically with electrochemical infrared reflection absorption spectroscopy, but also with other characterization methods such as single-crystal cyclic voltammetry, differential electrochemical mass spectrometry, or electrochemical scanning tunneling microscopy. We demonstrate the preparation in UHV, the transfer in inert atmosphere, and the immersion into the electrolyte for a complex model catalyst that requires surface science methods for preparation. Specifically, we study Pt nanoparticles supported on well-ordered Co₃O₄(111) films which are grown on an Ir(100) single crystal. In comparison with reference experiments on Pt(111), the model catalyst shows a remarkably different adsorption and reaction behavior during CO electrooxidation in alkaline environments.