Electrochemical measurement of the oxygen diffusivity and solubility in concentrated alkaline media on rotating ring-disk and disk electrodes—application to industrial chlorine-soda electrolyte

Chatenet, Marian; Aurousseau, M; Durand, Robert

doi:10.1016/s0013-4686(00)00325-x

Cited by 30 publications

(12 citation statements)

References 7 publications

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“…A mean value was used as the average of O 2 concentrations reported in the literature (1.03×10 −6 mol cm −3 in acid medium [27] and 0.835 × 10 −6 mol cm −3 in alkaline medium [28]). We can conclude that the oxygen reduction reaction on Pt is accomplished through a four-electron process, with some production of hydrogen peroxide as an intermediate only on bulk Pt, but not on the Pt nanoparticle-based electrode.…”

Section: O 2 Electroreduction On Pt-based Catalystsmentioning

confidence: 99%

Oxygen Electroreduction Catalyzed by Bilirubin Oxidase Does Not Release Hydrogen Peroxide

et al. 2011

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This paper reports on the electroreduction of oxygen catalyzed by bilirubin oxidase (BOD) without H 2 O 2 production. The enzyme was immobilized in a Nafion® matrix in the presence of either a commercial mediator, the 2,2′-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS), or a synthesized osmium redox complex to increase the kinetically slow bio-electroreaction. The use of a rotating ring-disk electrode system demonstrated for the first time the absence of hydrogen peroxide production during the oxygen reduction reaction at the active BOD centers mediated by ABTS. These results were compared with those obtained on Pt-based catalyst. We showed that BOD has the advantage to reduce O 2 at a smaller overpotential value (100 mV) than Pt (260 mV).

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Section: O 2 Electroreduction On Pt-based Catalystsmentioning

confidence: 99%

Oxygen Electroreduction Catalyzed by Bilirubin Oxidase Does Not Release Hydrogen Peroxide

et al. 2011

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“…D is the diffusion coefficient of O 2 in the electrolyte (1.65 · 10 À5 cm 2 s À1 ), m the kinematic viscosity of the electrolyte (1.19 · 10 À2 cm 2 s À1 ), C 0 the bulk concentration of O 2 (1.03 · 10 À3 mol L À1 ), X the rotation rate of the electrode, n the number of exchanged electron per O 2 molecule (close to 4) and 0.2 a coefficient used when X is expressed in rpm [14,28,29]. Then, the Tafel equation is:…”

Section: Comparison Of the Electrochemical Activity Towards Orr Of A-mentioning

confidence: 99%

How does α-FePc catalysts dispersed onto high specific surface carbon support work towards oxygen reduction reaction (orr)?

Baranton

Coutanceau

Garnier

et al. 2006

Journal of Electroanalytical Chemistry

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“…10,11 The CVs were collected at 3.8 bar (abs) cell pressure, since the pressure of Argon increases with temperature. In the next step, additional 10 bar of oxygen were filled into the cell yielding a total cell pressure of 13.8 bar (abs).…”

Section: Methodsmentioning

confidence: 99%

Design and Application of External Reference Electrode for Kinetic Studies at Elevated Temperatures and Pressures

Fleige

Wiberg

Arenz

2017

J. Electrochem. Soc.

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We present the design and application of an external reference electrode (RE) system for kinetic studies of the oxygen reduction reaction (ORR), the cathode process in high temperature proton exchange membrane fuel cells (HT-PEMFCs), at elevated temperatures and pressures inside an autoclave. The RE system comprises a solid ion-conducting junction based on Nafion tubing. External RE was a reversible hydrogen electrode (RHE) calibrated reproducibly relative to an internal RHE with an uncertainty <±5 mV over the temperature range of 25-170 • C. Functionality of the RE system was tested by measuring ORR in concentrated H 3 PO 4 relative to a calibrated external RHE. Thus, we are confident that the development is a useful and versatile tool for kinetic studies at elevated temperatures and pressures. Fast and reliable testing of fuel cell catalysts at relevant conditions is of high importance for academia and industry alike. Recently, we introduced an elevated pressure and temperature rotating disk electrode (RDE) system that allows electrocatalytic measurements under well-defined mass transport conditions 1,2 . The setup comprised an internal silver wire RE that enabled a stable determination of the reference potential, but the obtained calibration relative to an internal RHE lacked the required accuracy (< ± 5 mV) for accurate kinetic measurements. We therefore avoided in our previous work the determination of absolute kinetic rates of the ORR at elevated temperature and pressure. An approach to more reliable reference potentials in pressurized cells is to use external RE configurations.3 Recently, external RE systems for fuel cells with solid ion-conducting junctions based on Nafion tubing or the PBI/H 3 PO 4 polymer were published. 4,5Here we present the design and test of an external RE system with solid junction specifically developed for pressurized electrochemical cells. The most meaningful RE to study ORR with respect to fuel cells is the RHE, which is a hydrogen electrode immersed in the same electrolyte and at 1 bar H 2 partial pressure. 6 Thus, we applied an external RHE and calibrated it separately relative to an internal RHE, as its determination in situ 7,8 is not practical in pressurized cells. Application of the calibrated external RE was tested for studying ORR in conc. H 3 PO 4 at elevated temperatures. Such conditions are highly relevant for high temperature proton exchange membrane fuel cells (HT-PEMFC), but usually not accessible to RDE studies due to the low oxygen solubility in the electrolyte. The results demonstrate that our development enables meaningful kinetic studies in pressurized cells and thereby overcomes the significant accuracy issues related to internal REs operated at elevated temperatures. ExperimentalThe electrolyte used in this study was 85 wt% H 3 PO 4 (Suprapur, Merck). The gases used were supplied from gas cylinders (Air Liquide, Denmark) and had a purity of at least 99.995%. The electrochemical cell was placed inside an autoclave as described previously.

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Electrochemical measurement of the oxygen diffusivity and solubility in concentrated alkaline media on rotating ring-disk and disk electrodes—application to industrial chlorine-soda electrolyte

Cited by 30 publications

References 7 publications

Oxygen Electroreduction Catalyzed by Bilirubin Oxidase Does Not Release Hydrogen Peroxide

Oxygen Electroreduction Catalyzed by Bilirubin Oxidase Does Not Release Hydrogen Peroxide

How does α-FePc catalysts dispersed onto high specific surface carbon support work towards oxygen reduction reaction (orr)?

Design and Application of External Reference Electrode for Kinetic Studies at Elevated Temperatures and Pressures

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