Ruddlesden --- Popper Phases LaSrM¹_1-xM²_xO_4±δ (M¹, M²--Fe, Co, Ni) as a Promising Electrocatalyst for the Reactions of Oxygen Evolution and Urea Oxidation

Abstract

Ruddlesden --- Popper phases (RP) LaSrM¹_1-xM²_xO_4±δ (M¹, M²--Fe, Co, Ni), which are a type of perovskites, possess high catalytic activity at anodic potentials. Due to the low overvoltage of the oxygen evolution reaction (OER), they potentially can be used as anode materials in the process of electrochemical hydrogen production. Reducing the voltage on the electrolyzer will significantly reduce energy costs for producing highly pure hydrogen. It has been found that RP oxides prepared by spray pyrolysis of aqueous solutions containing nitrates of the corresponding metals have high phase purity and reproducible electrochemical characteristics. The catalytic activity of RP phases in OER decreases in the following series La_0.5Sr_1.5Ni_0.5Fe_0.5O₄ (LSNF) > La_0.5Sr_1.5Co_0.5Fe_0.5O₄ (LSCF) > La_0.5Sr_1.5Co_0.5Ni_0.5O₄ (LSCN), i.e., catalysts containing iron species are the most active. During the electrolysis process, Fe(III) compounds are concentrated at the electrode surface, which is the cause for their high catalytic activity in OER. The OER currents are stable over time in a 5.0 M KOH solution for all studied RP phases. Another approach to reduce the voltage of a hydrogen electrolyzer is to replace the OER with another reaction that occurs at less positive electrode potentials. Such a reaction may be electrochemical oxidation of urea (UOR). It has been found that the sequence of decrease in the catalytic activity of RP phases in UOR is different compared to OER, namely LSCF > LSCN > LSNF. It has been proven that a sharp decrease in UOR currents over time occurring under potentiostatic conditions, is due to the formation of a layer of insoluble carbonates, which are products of urea oxidation, at the electrode surface. The inhibitory effect of carbonates can be significantly diminished by increasing their solubility in solutions subjected to electrolysis. This can be done either by replacing KOH solutions with CsOH solutions or by heating KOH solutions. It has been shown that sustainable electrooxidation of urea is possible at T > 60 °C, which corresponds to the operating mode of industrial filter press electrolyzers

The work was carried out with the financial support of the Russian Science Foundation (grant no. 21-13-00419)

Please cite this article in English as:

Sinitsyn P.A., Kuznetsov V.V., Levchenko S.V., et al. Ruddlesden --- Popper phases LaSrM¹_1-xM²_xO_4±δ (M¹, M²--Fe, Co, Ni) as a promising electrocatalyst for the reactions of oxygen evolution and urea oxidation. Herald of the Bauman Moscow State Technical University, Series Natural Sciences, 2024, no. 6 (117), pp. 103--123 (in Russ.). EDN: AFQQAS

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