Perovskite oxides are versatile materials due to their wide variety of compositions offering promising catalytic properties, especially in oxidation reactions. In the presented study, LaFe1−xCoxO3 perovskites were synthesized by hydroxycarbonate precursor co-precipitation and thermal decomposition thereof. Precursor and calcined materials were studied by scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TG), and X-ray powder diffraction (XRD). The calcined catalysts were in addition studied by transmission electron microscopy (TEM) and N2 physisorption. The obtained perovskites were applied as catalysts in transient CO oxidation, and in operando studies of CO oxidation in diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). A pronounced increase in activity was already observed by incorporating 5% cobalt into the structure, which continued, though not linearly, at higher loadings. This could be most likely due to the enhanced redox properties as inferred by H2-temperature programmed reduction (H2-TPR). Catalysts with higher Co contents showing higher activities suffered less from surface deactivation related to carbonate poisoning. Despite the similarity in the crystalline structures upon Co incorporation, we observed a different promotion or suppression of various carbonate-related bands, which could indicate different surface properties of the catalysts, subsequently resulting in the observed non-linear CO oxidation activity trend at higher Co contents.
Mixed Cu‐Co hydroxycarbonates of the type (Cu1–xCox)2CO3(OH)2 have been synthesized over the whole range of Cu‐Co substitution (0≤x≤1) by co‐precipitation and their electrocatalytic activity in the oxidation reactions of ethanol (EOR), ethylene glycol (EGOR) and glycerol (GOR) in alkaline environment was evaluated to retrieve composition–activity correlations. Generally, cobalt incorporation led to higher activities for the alcohol oxidation (AOR) compared to the Cu‐only material and the results are compared with the competing oxygen evolution reaction (OER). On the Cu‐Co hydroxycarbonates, the electrooxidation of vicinal alcohols such as glycerol and ethylene glycol requires lower overpotentials than EOR and OER. Cu leaching from the hydroxycarbonate structure was observed in the presence of vicinal alcohols. The impact of chemical and electrochemical leaching of copper from the catalysts has been studied. The chemically leached catalyst was found to show increased AOR activity compared to other hydroxycarbonates, enabling the formation of larger amounts of formic acid during GOR measured in a circular flow cell electrolyzer. The results highlight that Cu‐Co hydroxycarbonates can be used as precursors to generate electrocatalytically active materials from Cu‐Co hydroxycarbonates for the AOR in alkaline solution.
Hydrogen generated in electrolyzers is discussed as a key element in future energy scenarios, but oxygen evolution as the standard anode reaction is a complex multi‐step reaction requiring a high overpotential. At the same time,it does not add value‐the oxygen is typically released into the atmosphere. Alternative anode reactions which can proceed at similar current densities as the hydrogen evolution are, therefore, of highest interest. We have discovered a high‐performance electrode based on earth‐abundant elements synthesized in the presence of H
2
O
2
, which is able to sustain current densities of close to 1 A cm
−2
for the oxidation of many organic molecules, which are partly needed at high production volumes. Such anode reactions could generate additional revenue streams, which help to solve one of the most important problems in the transition to renewable energy systems, i.e. the cost of hydrogen electrolysis.
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