Electrochemical stability of RuO2(110)/Ru(0001) model electrodes in the oxygen and chlorine evolution reactions

Andrey Goryachev, Marco Etzi Coller Pascuzzi, Francesco Carlà, Tim Weber, Herbert Over (Corresponding author), Emiel J.M. Hensen (Corresponding author), Jan Philipp Hofmann (Corresponding author)

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Abstract

RuO 2 is commercially employed as an anodic catalyst in the chlor-alkali process. It is also one of the most active electrocatalysts for the oxidation of water, relevant to electrochemical water splitting. However, the use of RuO 2 is limited by its low anodic stability under acidic conditions, especially at high overpotentials. In the present work, the electrochemical stability of model RuO 2(110)/Ru(0001) anodes was investigated in order to gain a deeper understanding of the relation between structure and performance in Cl 2 and O 2 evolution reactions (CER and OER, respectively). Online electrochemical mass spectrometry was used to determine the onset potential of CER and OER in HCl and H 2SO 4 electrolytes, respectively. The onset potential of OER was higher in HCl than in H 2SO 4 due to competition with the kinetically more favorable CER. A detailed stability evaluation revealed pitting corrosion of the electrode surface with exposure of Ru(0001) metal substrate concomitant with the formation of a hydrous RuO 2 in some areas regardless of the applied electrochemical treatment. However, despite local pitting, the RuO 2(110) layer preserves its thickness in most areas. Degradation of the electrode was found to be less severe in 0.5 M HCl due to a decrease in the faradaic efficiency of RuO 2 oxidation caused by competition with the kinetically more favorable CER.

Original languageEnglish
Article number135713
Number of pages11
JournalElectrochimica Acta
Volume336
DOIs
Publication statusPublished - 10 Mar 2020

Funding

The authors thank ESRF for technical and financial support during beam time IHCH-1283 at beamline ID03. Dr. Iman Sohrabnejad-Eskan of JLU Giessen and Dr. Johannes Pfrommer of DESY Hamburg are acknowledged for technical support and fruitful discussions. The authors would like to thank the following colleagues of Eindhoven University of Technology: Ad H. Wonders for useful discussions and assistance with the OLEMS measurements; Adelheid M. Elemans-Mehring for ICP-OES measurements; Alexey Bolshakov for assistance on synchrotron measurements. A.G. and E.J.M.H. acknowledge funding by the Dutch Research School Combination Catalysis Controlled by Chemical Design (NRSC-Catalysis) and an NWO Vici grant. M.E.C.P. acknowledges funding by a Graduate School program from the Netherlands Organization for Scientific Research ( NWO ). H.O. thanks BMBF (project: 05K2016-HEXCHEM ) and DFG ( Ov21-16 within SPP2080) for financial support. The authors thank ESRF for technical and financial support during beam time IHCH-1283 at beamline ID03. Dr. Iman Sohrabnejad-Eskan of JLU Giessen and Dr. Johannes Pfrommer of DESY Hamburg are acknowledged for technical support and fruitful discussions. The authors would like to thank the following colleagues of Eindhoven University of Technology: Ad H. Wonders for useful discussions and assistance with the OLEMS measurements; Adelheid M. Elemans-Mehring for ICP-OES measurements; Alexey Bolshakov for assistance on synchrotron measurements. A.G. and E.J.M.H. acknowledge funding by the Dutch Research School Combination Catalysis Controlled by Chemical Design (NRSC-Catalysis) and an NWO Vici grant. M.E.C.P. acknowledges funding by a Graduate School program from the Netherlands Organization for Scientific Research (NWO). H.O. thanks BMBF (project: 05K2016-HEXCHEM) and DFG (Ov21-16 within SPP2080) for financial support.

FundersFunder number
Dutch Research School Combination Catalysis Controlled by Chemical Design
NRSC-Catalysis
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Deutsche ForschungsgemeinschaftOv21-16, SPP2080
European Synchrotron Radiation Facility
Bundesministerium für Bildung und Forschung05K2016-HEXCHEM
Eindhoven University of Technology
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Bundesministerium für Bildung und Frauen

    Keywords

    • Chlorine evolution reaction
    • Electrocatalysis
    • Oxygen evolution reaction
    • Ruthenium dioxide
    • Stability

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