Electrooxidation of Alcohols on Mixed Copper–Cobalt Hydroxycarbonates in Alkaline Solution. Issue 13 (10th June 2022)

• Record Type: Journal Article
• Authors: Braun, Michael; Behrendt, Gereon; Krebs, Moritz L.; Dimitri, Patricia; Kumar, Piyush; Sanjuán, Ignacio; Cychy, Steffen; Brix, Ann Cathrin; Morales, Dulce M.; Hörlöck, Jennifer; Hartke, Bernd; Muhler, Martin; Schuhmann, Wolfgang; Behrens, Malte; Andronescu, Corina
• Is Part Of: ChemElectroChem. Volume 9:Issue 13(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-10
• Subjects: Alcohols -- Alkaline electrolyte -- Electrocatalytic alcohol oxidation -- Electrochemistry -- Hydroxycarbonates; Electrochemistry -- Periodicals; 541.37
• DOI: 10.1002/celc.202200267
• Languages: English
• ISSNs: 2196-0216

Abstract

Abstract: Mixed Cu‐Co hydroxycarbonates of the type (Cu1– x Co x )2 CO3 (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. Abstract : Replacing the oxygen evolution reaction at the anode by the oxidation of alcohols such as glycerol to value‐added products can make green hydrogen production by electrochemical water splitting economically feasible. For the first time, a series of low‐cost 3d transition metal‐based mixed Cu and Co hydroxycarbonates was prepared and investigated as electrocatalysts for the oxidation of glycerol, ethylene glycol, and ethanol.