Proceedings of MATSUS Spring 2024 Conference (MATSUS24)
Publication date: 18th December 2023
There is an urgent need to develop new technologies and more stable catalysts that selectively and efficiently convert the CO2 [1]. Copper (Cu) has demonstrated to be a promising catalyst for as it reduces the CO2 beyond CO producing valuable fuels and chemicals [2]. However, the product selectivity is low on copper. The product distribution shows a strong dependence on the different copper crystalline facets and the electroactive surface area [2,3]. This emphasises the need to apply different methods to characterise the copper surface structure and address its facet distribution, to obtain a more selective catalyst.
In this work we have use Lead (Pb) under potential deposition (UPD) to characterize different copper surfaces that have been reconstructed using an electro-roughening method in electrolytes containing chloride (Cl-) or fluoride (F-) anions. The Lead UPD allows to characterize the different crystalline orientations and the electroactive area on copper surfaces [4]. To modify the copper surfaces in the presence of both halides, we carried out an electrochemical roughening treatment at different voltage limits and by modifying the number of voltametric cycles. This process shows that the degree of restructuration on the copper polycrystal surfaces (Figure 1a) depends on the type of halide. Chloride induces n(100)x(110) domains (Figure 1b). In contrast, fluoride only introduces disorder and increases the electroactive surface area (Figure 1c). Measurements with x-ray photoelectron spectroscopy (XPS), carried out after the roughening treatment but before removing the oxide or halide layer, shows that chloride strongly adsorbs on copper whereas we only detected traces of fluoride, suggesting that fluoride weakly adsorbs on copper.
Figure 1. Lead UPD Cyclic Voltammetry (Top side) and Scanning Electron Microscopy images (Bottom side) of a) a polycrystalline copper surface, b) a reconstructed copper surface in NaCl, and c) a reconstructed copper surface in NaF.
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