Ruthenium Oxide Cathodes for Chlor-Alkali Electrolysis

Hachiya, Toshinori; Sasaki, Takaharu; Tsuchida, Kazuyuki; Houda, Hiroyoshi

doi:10.1149/1.3104645

Cited by 8 publications

(7 citation statements)

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“…280.1 eV. This second peak has been attributed to metallic Ru by Näslund et al, which agrees with results from measurements on Ru (0001) performed by Over et al Hachiya et al have also reported formation of metallic Ru in RuO 2 electrodes used for HER at −6 kA/m 2 . In that case, however, the Ru diffraction pattern was only observed after electrolysis for 180 days but not after electrolysis for 30 days (30 times longer than in the work of Näslund et al).…”

Section: Resultssupporting

confidence: 87%

“…In contrast, based on in situ XRD, Chabanier et al concluded that bulk conversion of RuO 2 into metallic Ru does not occur during HER, and Rochefort et al found formation of metallic Ru in the surface unlikely based on XPS measurements. A possible explanation for the differences could be that the electrodes in the studies of Chabanier et al and Rochefort et al were subjected to a lower HER current density and for a significantly shorter time (1 to 2 h) than the electrodes in the studies of Näslund et al and Hachiya et al…”

Section: Resultssupporting

confidence: 74%

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Structural Changes in RuO₂ during Electrochemical Hydrogen Evolution

2016

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A comprehensive theoretical study of the X-ray photoelectron shifts for RuO 2 during hydrogen evolution has been performed. The shifts have been calculated using firstprinciples density functional theory and are compared with previous theoretical and experimental results to reconsider the proposed structural changes occurring during hydrogen evolution on RuO 2 . We find that during hydrogen evolution hydrogen enters the rutile RuO 2 lattice and converts oxygen groups into hydroxyl groups and that this process explains the experimentally observed increase in unit cell dimensions as well as observed chemical shifts. Furthermore, carbon contamination is the most likely explanation for a set of peaks previously identified as caused by a new RuO(OH) 2 phase. We find that formation of metallic Ru is just one possible explanation for another peak in the X-ray photoelectron spectrum and that explanations including conversion of RuO 2 into Ru(OH) 3 , or removal of oxygen from Ru active surface sites, also can explain the observed shifts.

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Section: Resultssupporting

confidence: 87%

Section: Resultssupporting

confidence: 74%

Structural Changes in RuO₂ during Electrochemical Hydrogen Evolution

2016

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“…For strongly alkaline conditions (8−10 M NaOH), this view has been experimentally confirmed. For RuO 2 /Ni cathodes, a hydroxylation process is reported, 194,195 forming first a ruthenium oxyhydroxide phase. Extensive treatment in the HER potential region further transforms the hydrous RuO 2 to metallic Ru.…”

Section: Critical Discussion Of Selected Model Studiesmentioning

confidence: 99%

Fundamental Studies of Planar Single-Crystalline Oxide Model Electrodes (RuO₂, IrO₂) for Acidic Water Splitting

Over

2021

ACS Catal.

178

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Electrocatalytic water splitting allows storing excess energy from renewable energy sources such as wind and solar in chemical bonds of hydrogen molecules. So far, only polymer electrolyte membrane (PEM) water electrolyzers under acidic conditions can cope with the intermittent supply of energy, requiring, however, noble metals at the cathode for the hydrogen (HER) and precious metal oxides at the anode for the oxygen evolution reaction (OER). Prototypical oxides for the OER under acidic conditions are RuO2 and IrO2 that can meet the stringent requirements for long-term stability and high electrocatalytic activity. While RuO2 is substantially more active than IrO2, RuO2 is significantly less stable than IrO2 due to corrosion under OER conditions. Our microscopic understanding of the underlying processes of corrosion is, however, surprisingly poor, while the rate-determining steps in the OER over RuO2 and IrO2 are still under debate. In this perspective, I will be focusing on the discussion of the electrochemical degradation of ultrathin single-crystalline RuO2(110) and IrO2(110) films in the potential regions of both OER and HER. The single crystallinity of the model electrodes allows for identifying structure–property relationships and for a tight connection to theory. Since stability and activity in the OER are reported to be intimately coupled, I will also include a critical review of our present knowledge on the microscopic steps in the OER on RuO2 and IrO2, both from theory and experiments. Ultimately, from these atomic scale insights, the inherent material properties may be uncovered which underlie the observed electrochemical stability and activity of IrO2 and RuO2. It is the hope that these fundamental insights will aid the search for alternative more abundant electrode material systems for acidic water electrolyzers.

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“…Likewise, microcrystals (Needlelike structure) were observed from 2 to 5 µm wide such as the CeO 2 deposits obtained by electrochemical generation (Figures 5) (Zhou and Switzer, 1996;Zhou et al, 1995). Hachiya et al (2009), synthesized cathodes to obtain sodium hydroxides by the chloralkali process, using a mixture of RuCl 3 and CeCl 3 supported on a Ni mesh, incinerated at 550 °C to obtain RuO 2 and CeO 2 . The cathode electron micrographs show a similar morphology regarding Figure 5d; there were presence of microcrystals, using a cathode in an electrolytic cell, and it was similar to this work.…”

Section: Characterization Of Cerium Oxide Deposit In a Mes Configurationmentioning

confidence: 99%

Microbial electrochemical system for obtaining value-added products using a halotolerant bioanode

González¹,

Escobar²,

Tapia-Tussell³

et al. 2021

RMIQ

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Ruthenium Oxide Cathodes for Chlor-Alkali Electrolysis

Cited by 8 publications

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Structural Changes in RuO₂ during Electrochemical Hydrogen Evolution

Structural Changes in RuO₂ during Electrochemical Hydrogen Evolution

Fundamental Studies of Planar Single-Crystalline Oxide Model Electrodes (RuO₂, IrO₂) for Acidic Water Splitting

Microbial electrochemical system for obtaining value-added products using a halotolerant bioanode

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Ruthenium Oxide Cathodes for Chlor-Alkali Electrolysis

Cited by 8 publications

References 0 publications

Structural Changes in RuO2 during Electrochemical Hydrogen Evolution

Structural Changes in RuO2 during Electrochemical Hydrogen Evolution

Fundamental Studies of Planar Single-Crystalline Oxide Model Electrodes (RuO2, IrO2) for Acidic Water Splitting

Microbial electrochemical system for obtaining value-added products using a halotolerant bioanode

Contact Info

Product

Resources

About

Structural Changes in RuO₂ during Electrochemical Hydrogen Evolution

Structural Changes in RuO₂ during Electrochemical Hydrogen Evolution

Fundamental Studies of Planar Single-Crystalline Oxide Model Electrodes (RuO₂, IrO₂) for Acidic Water Splitting