Hydrodynamic methods II

Victoria Nikitina
Skoltech

1
Oxygen reduction reaction mechanism with RRDE

• Direct 4-e pathway from O2 to H2O or OH-

• 2-e pathway to form H2O2 or HO2- with reduction to H2O or OH-
• Chemical decomposition of H2O2 or HO2-

2
 2/3
𝐵𝑂2 = 0.62𝐷𝑂2 𝜈 −1/6
2/3
𝐵𝐻2𝑂2 = 0.62𝐷𝐻2𝑂2 𝜈 −1/6

1 1
Mass balance for O2: 𝐵𝑂2 𝜔 2 (𝐶𝑂∗2 − 𝐶𝑂𝑠2 ) = (𝑘1 + 𝑘2 )𝐶𝑂𝑠2 𝐶𝑂𝑠2 𝐵𝐻2𝑂2 𝜔 2 + 𝑘3
1 =
Mass balance for H2O2: 𝐵𝐻 𝑂 𝜔 2 𝐶𝐻𝑠 𝑂 = 𝑘2 𝐶𝑂𝑠2 − 𝑘3 𝐶𝐻𝑠2𝑂2 𝐶𝐻𝑠2𝑂2 𝑘2
2 2 2 2

Total current at the disk: 𝐼𝐷 = 4𝐹𝜋𝑟12 𝑘1 𝐶𝑂𝑠2 + 2𝐹𝜋𝑟12 𝑘2 𝐶𝑂𝑠2 + 2𝐹𝜋𝑟12 𝑘3 𝐶𝐻𝑠2𝑂2
1
Diffusion current for H2O2 removal from the disk electrode: 𝐼𝐷,𝐻2𝑂2 = 2𝐹𝜋𝑟1 𝐵𝐻2𝑂2 𝜔 2 𝐶𝐻𝑠2𝑂2
2

1
Current at the ring electrode: 𝐼𝑅 = 𝐼𝐷,𝐻2𝑂2 𝑁 = 2𝐹𝜋𝑟1 𝐵𝐻2𝑂2 𝜔 2 𝐶𝐻𝑠2𝑂2
2
𝑁

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Oxygen reduction at oxide-
free Pt electrodes in H2SO4

𝐼𝐷 1 2𝑘1 2𝑘3 𝑘1 1
−2
= 1+ + 1+ 𝜔
𝐼𝑅 𝑁 𝑘2 𝐵𝐻2𝑂2 𝑁 𝑘2

I. k3 is very small
Produced peroxide cannot be reduced to H2O
1
𝐼𝐷 −2
Slope of vs. 𝜔 is zero
𝐼𝑅
Intercept gives k1/k2
Damjanovic A, Genshaw MA, Bockris JO’M. The role of hydrogen peroxide in
the reduction of oxygen at platinum electrodes. J Phys Chem 1966;70(11):3761.
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 Oxygen reduction at Pt
electrodes in KOH

𝐼𝐷 1 2𝑘1 2𝑘3 𝑘1 1
−2
= 1+ + 1+ 𝜔
𝐼𝑅 𝑁 𝑘2 𝐵𝐻2𝑂2 𝑁 𝑘2

II. k3 is moderately high

1
𝐼𝐷 −2
Plots of vs. 𝜔 give straight lines
𝐼𝑅
1 2𝑘1
Intercept gives 1+
𝑁 𝑘2
2𝑘3 𝑘
Slope gives 1+ 1
𝐵𝐻2𝑂2 𝑁 𝑘2
Possible to estimate 𝑘3
Damjanovic A, Genshaw MA, Bockris JO’M. The role of hydrogen peroxide in 5
the reduction of oxygen at platinum electrodes. J Phys Chem 1966;70(11):3761.
 𝐼𝐷 1 2𝑘1 2𝑘3 𝑘1 1
−2
= 1+ + 1+ 𝜔
𝐼𝑅 𝑁 𝑘2 𝐵𝐻2𝑂2 𝑁 𝑘2

III. k2 >> k1
1
𝐼𝐷 −2
Intercept of vs. 𝜔 is close to 1/N
𝐼𝑅

IV. k1 >> k2
V. Mixed 4e and 2e process
𝐼𝑅 → 0
𝐼𝐷,𝑙,𝑂2 − 𝐼𝐷 1 2𝑘3 𝐵𝑂2 2𝐵𝑂2 −1
1 = 1+ + 𝜔 2
𝐼𝐷,𝑂2 = 4𝐹𝜋𝑟1 𝐵𝑂2 𝜔 2 𝐶𝑂∗2
2 𝐼𝑅 𝑁 𝑘2 𝐵𝐻2𝑂2 𝑘2 𝑁

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More complex ORR mechanisms

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 More complex ORR mechanisms

Chemical step!

8
Rotation rate current dependence to distinguish
chemical steps from electrochemical steps

H2O2 reduction/oxidation on some Mn oxides

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Effective number of electrons transferred per O2 molecule
n is calculated from Koutecky-Levich slopes

1 1 1
= +
𝑖 𝑖𝐾 0.62𝑛𝐹𝐴𝐷2/3 𝜔1/2 𝜈 −1/6 𝐶𝑂∗
𝑂

Limiting diffusion
current

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ORR on La1-xSrxCoO3-δ

11
 Sulfur reduction in Li-S batteries

initial electrochemical
step
disproportionation
reactions

12
J. Phys. Chem. C 2014, 118, 5733−5741
Proposed sulfur reduction mechanism

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 RRDE for oxygen evolution

• Epitaxial La0.6Sr0.4MnO3 grown on

Nb:SrTiO3 to study the mechanism of OER

J. Phys. Chem. C 2016, 120, 27746−27756 14

• Oxygen is produced at the disk and gets reduced at the ring
• Tafel slope of ca. 60 mV/decade – consistent with EC mechanism
(rate-determining chemical step)
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 Superoxide Radical Stability in Aprotic Li−Air Batteries
• Problem:
poor stability of the electrolyte due to its
reaction with the superoxide radical
(O2•−) produced upon discharge at the battery’s
cathode.

• Mass-transport-limited current derived from the

oxidation of electrochemically generated
superoxide radical at the disk electrode is used to
quantify the amount of O2-. O2- diffuses from the
disk to the ring electrode and gets oxidized there.

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 Advanced way to study electrocatalytic reactions mechanisms

Parameters:
Rate constants, adsorbate interaction
constants, transfer coefficients, diffusion
coefficients, active sites density, diffusion
layer thickness, etc.

ChemElectroChem 2016, 3, 1667 – 1677 17

Experiment vs. numerical modeling

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19
 Electrochemical ESR with hydrodynamic methods
• Electropolymerisation of maleimide
• Variation of the diffusion limited
current with the flow rate
Channel electrode

in ESR spectrometer

• ESR spectrum of maleimide radical anion

• At low flow rates ESR signal is lower – the ESR intensity vs. flow rate
radical decomposes
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 High-speed channel electrode to study ET kinetics
• Solution is pumped at speeds approaching 50 m/s over a microband
electrode of length 1-10 μm so as to attain a mass transport coefficient
of ca. 1 cm/s

1.6 cm/s

0.8 cm/s

0.60 cm/s

Levich plot

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J. Electroanal. Chem. 534 (2002) 151-161