Operando X-Ray Diffraction Studies of Co Oxide Model Catalysts during Alcohol Oxidation and Oxygen Evolution Reaction

Abstract

Green energy technology involving hydrogen generation requires developing catalyst materials of commercial viability, good stability and high reactivity for the electrochemical water splitting. Transition-metal oxides such as Co3O4 are among the best precious-metal-free electrode materials for the anodic oxygen evolution reaction (OER) in alkaline electrolysis [1]. Moreover, these spinel-type transition metal oxides are an important class of catalysts for the selective oxidation of organic compounds. Previous in situ and operando surface X-ray diffraction studies of epitaxial Co oxide films by our group showed pronounced changes in the near-surface structure of these catalysts. In particular, a sub-nm CoOx(OH)y skin layer starts forming in the pre-OER potential range which is accompanied by a volume change of the Co3O4 lattice [2]. In a more recent work, where we systematically explored the relationship between the effective thickness of this skin layer and the OER activity, we found clear evidence that the entire skin layer serves as a three-dimensional reactive zone for the OER [3]. Since the skin layer formation already starts several 100 mV negative of the onset of the OER, it is not induced by the catalytic reaction itself, but rather reflects the oxides’ electrochemistry, and may thus be expected also for other electrocatalytic processes, especially other electrocatalytic oxidation reactions which occur in a similar potential range. These oxide materials are not only of interest for OER, but also for the electrochemical oxidation of other compounds, such as alcohols [4]. However, data on the oxides’ structure in the presence of organic compounds does not exist at present. Obtaining such data is of great interest for understanding the mutual influence of oxide-electrolyte interface structure and electrocatalytic activity. In addition, the vast majority of publications on Co oxide oxidation processes, in particular all in situ and operando studies, have been performed up to now at room temperature only, and, thus, the catalytic performance of these materials at higher temperatures remains unknown. As electrolyzers and industrial (electro-) catalytic processes typically operate at elevated temperatures, such data are of considerable interest. Here, we present results of first potential-dependent structural studies of epitaxial Co3O4(111) and CoOOH(001) films electrodeposited on Au(111) single crystal substrates during ethylene glycol oxidation (EG Ox) in 0.1 M NaOH solution and compare those with the behavior found on the same samples in EG-free electrolyte. Ethylene glycol oxidation is a highly suitable reaction for such studies, as it occurs at potentials prior to the onset of the OER [4]. The samples were investigated as a function of electrode potential and temperature by operando surface X-ray diffraction at beamline P23 of PETRA III, DESY. The EG Ox was studied by successively increasing the EG concentration from 0 to 0.1, 0.5 and 2 M, which allows direct quantitative comparison of the potential-dependent structural changes. These studies of the oxides’ structure and electrochemical reactivity were performed at different temperatures in the range of 25 - 70°C. In all cases significant skin layer formation and accompanying changes in the oxide lattice strain were observed. The structural data are correlated with the results of cyclic voltammetry and optical reflectivity measurements that were recorded in parallel with the X-ray diffraction measurements. Together, they provide insights into the potential-dependent evolution of the skin layer thickness and strain and into the stability of the oxides in dependence of EG concentration and temperature. First results indicate that at elevated temperatures larger skin layer thicknesses and strain changes occur. Furthermore, the structural properties recover completely upon cooling back down to room temperature, suggesting that these effects are highly reversible. In the presence of EG, the reversible skin layer formation and changes in the Co3O4 bulk lattice were also observed, even though these structural changes appear to be less pronounced under alcohol oxidation conditions, especially at higher EG concentration. These studies will contribute to an in-depth understanding of the near surface structure of these Co oxide thin films during liquid phase oxidation catalysis, which is a prerequisite for the design of new, abundant and superior catalysts based on transition metal oxides for catalytic selective oxidation processes.We acknowledge financial support by the Deutsche Forschungsgemeinschaft via special research area TRR 247, project B10 (project no. 388390466).[1] A. Bergmann et al., Nature Catalysis 2018, 1, 711 - 719[2] F. Reikowski et al., ACS Catal. 2019, 9, 3811 - 3821[3] T. Wiegmann et al., ACS Catal. 2022 [4] S. N. Sun et al, J. Electrochem. Soc. 2016, 163, H99