Supporting information

Structure-Property Relationship of Bifunctional MnO2 Nanostructures:

Highly-Efficient, Ultra-Stable Electrochemical Water Oxidation and Oxygen

Reduction Reaction Catalysts Identified in Alkaline Media

Yongtao Menga, Wenqiao Songa, Hui Huanga, Zheng Renb, Sheng-Yu Chena and Steven L.

Suiba,b*

a
Department of Chemistry, University of Connecticut, 55 N. Eagleville Rd., Storrs, CT 06269-3060,

U.S.A. bInstitute of Materials Science and Department of Chemicals, Materials & Biolmolecular

Engineering, University of Connecticut, Storrs, CT 06269-3222,U.S.A. E-mail: steven.suib@uconn.edu

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Figure S1. Manganese oxide nanostructures (α-MnO2-SF, Ni/α-MnO2-SF, α-MnO2-HT, AMO,

β-MnO2, and δ-MnO2) catalyzed oxygen reduction and oxygen evolution reactions in 0.1 M

KOH. The closer potential gap between ORR and OER means better bifunctional catalytic

activities. The cathodic sweep was shown for ORR, and the anodic sweep was shown for the

OER. Both scan rates are at 5 mV s-1

Calculation of overpotential η, the conversion of E vs. SCE to E vs. RHE

E   1.230 V  0.059 VpH, pH of 0.1 M KOH= 13
E   1.230 V – 0.059  13  0.463 vs. RHE
SCE (saturated KCl) vs. RHE=0.244 V
E   0.463  0.244  0.219 V vs. SCE,
Overpotential η = E (vs. SCE)-0.219 V
E (vs. RHE) =E (vs. SCE) +(1.23-0.219)= E (vs. SCE)+1.01 V

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Figure S2. Scanning electron microscopy (SEM) images of manganese oxide nano structures (A)

α-MnO2-HT (B) α-MnO2-SF (C) Ni/α-MnO2-SF (D) AMO (E) β-MnO2 and (F) δ-MnO2.

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Figure S3. iR corrected rotating disk electrode voltammogram (RDEV) of oxygen evolution

reaction on α-MnO2-SF in the first continuous three-cycle sweeps at 5 mV s-1 scan rate and 1600

rpm in O2-saturated 0.1 M KOH. The first cycle was reported in Figure 4a and Figure 6a. The

horizontal dotted line represents the 10 mA cm-2. The activity did not show any drop in the first 3

cycles, suggesting good stability.

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Figure S4. iR corrected rotating disk electrode voltammograms (RDEV) of oxygen evolution

reactions on AMO in the first continuous three-cycle sweeps at 5 mV s-1 scan rate and 1600 rpm

in O2-saturated 0.1 M KOH. The first cycle was reported in Figure 4a. The OER activities show

a gradual drop between the 1st and 3rd cycles.

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Figure S5. iR corrected rotating disk electrode voltammograms (RDEV) of oxygen evolution

reactions on β-MnO2 in the first continuous three-cycle sweeps at 5 mV s-1 scan rate and 1600

rpm in O2-saturated 0.1 M KOH. The first cycle was reported in Figure 4a. The OER activities

show a significant drop between the 1st and the 2nd cycle.

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Figure S6. iR corrected rotating disk electrode voltammograms (RDEV) of oxygen evolution

reactions on δ-MnO2 for the first continuous three-cycle sweeps at 5 mV s-1 scan rates and 1600

rpm in O2-saturated 0.1 M KOH. The first cycle was reported in Figure 4a. The OER activities

showed dramatic and a constant drop between each cycle from the 1st to the 2nd, then from 2nd to

the 3rd cycle.

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Figure S7. iR corrected rotating disk electrode voltammograms (RDEV) of oxygen evolution

reactions on Ni/α-MnO2-SF in the first continuous three-cycle sweeps at 5 mV s-1 scan rates and

1600 rpm in O2-saturated 0.1 M KOH. The first cycle is reported in Figure 6a. The OER

activities showed a small degradation from the 1st to the 2nd cycle, but a high and stable activity

overall comparable to α-MnO2-SF, shown in Figure S3.

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Figure S8. iR corrected rotating disk electrode voltammograms (RDEV) of oxygen evolution
reactions on α-MnO2-HT in the first continuous three-cycle sweeps at 5 mV s-1 scan rates and
1600 rpm in O2-saturated 0.1 M KOH. The first cycle was reported in Figure 6a. The OER
activities did not show any degradation over cycles, although there is a 30 % smaller peak
current density than for α-MnO2-SF.

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Figure S9. HRTEM images of α-MnO2-SF and Ni/α-MnO2-SF before (a) and (c), and after
stability tests (b) and (d), respectively.

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Figure S10. LSV curves for ORR and corresponding K-L plots for manganese oxides: (A)

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α-MnO2-SF, (B) Ni/α-MnO2-SF, (C) α-MnO2-HT, (D) AMO, (E) β-MnO2 and (F) δ-MnO2.
To interpret the ORR results, Koutechy-Levich(K-L) plots were applied on the basis of the
following equation.

1 1 1 1 1
= + =− 0
− 2/3
i ik id l nFAkC 0.62nFADO2 v −1 / 6C 0 ω 1/ 2

where ik is the kinetic current; idl is the diffusion limiting current; n is the overall number of

electrons transferred; F is the Faraday constant (96500 C mol-1); A is the geometric electrode

area (0.165 cm2); k is the rate constant for oxygen reduction; C0 is the saturated concentration of

oxygen in 0.1 M KOH (1.2×10-6 mol cm-3); DO2 is the diffusion coefficient of oxygen (1.73×10-5

cm2 s-1); ν is the kinetic viscosity of electrolyte (0.01 cm2 s-1); and ω is the rotation rate of the

electrode (rad s-1).

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Table S1. XPS results for △E2p1/2, △E3s splitting, O 1s and AOS from binding energies (BE)
for deconvoluted components of the O 1s region.

Samples △E 2p1/2 △E 3s AOSa O 1s (eV)

BE(eV) area(%)

α-MnO2-SF 11.9 4.6 3.71(3.79)b Mn-O-Mn 529.5 72.8

Mn-OH 531.3 20.9

H-O-H 533.4 6.3

Ni/α-MnO2-SF 11.9 4.7 3.69 Mn-O-Mn 529.5 70.8

Mn-OH 531.4 22.3

H-O-H 533.4 6.9

α-MnO2-HT 11.9 4.7 3.66 Mn-O-Mn 529.5 65.9

Mn-OH 531.6 22.7

H-O-H 533.7 11.4

AMO 11.4 4.8 3.68(3.91)b Mn-O-Mn 529.5 70.8

Mn-OH 531.3 22.9

H-O-H 533.5 6.3

β-MnO2c 11.6 4.4 - - - -

δ-MnO2 11.4 4.5 3.69(3.63)b Mn-O-Mn 529.6 70.6

Mn-OH 531.6 22.1

H-O-H 533.5 7.3

a. The average oxidation states(AOS) of Mn can be estimated from O1s core level spectra from
XPS results on the basis of the intensities of Mn-O-Mn, Mn-OH components, using the
following equation1:

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  !"! # !"$ %& !"$ 
AOS 
 !"!

IMn-O-Mn stands for the contribution from both MnOOH and MnO2, whereas IMn-OH represents the
contribution from hydroxyl groups.
b. Data in parenthesis were obtained from a reference sample.
c. AOS for β-MnO2 using the above formula produces large error (AOS=3.2 ) due to the effect
of physically adsorbed moisture under atmosphere, and thus was not adopted.
The high-resolution XPS spectra of Mn 3s and Mn 2p region were carefully collected by
sweeping more than 400 repeats for all the samples. The XPS spectra obtained were analyzed
and fitted using CasaXPS software (version 2.3.12). The C 1s photoelectron line at 284.6 eV was
used as a reference for correction of the surface charging. A mixture of Gaussian (70%) and
Lorentzian (30%) functions was used for the least-squares curve fitting procedure.

(1) M. Toupin, T. Brousse and D. Bélanger, Chem. Mater., 2004, 16, 3184-3190

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Figure S11. XPS O 1s regions of manganese oxide nanostructures. Raw data are shown by dots,

and the fitted data are shown as solid lines. All the spectra were calibrated to the C 1s transition

set at 284.6 eV.

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Figure S12. Mn 3s splitting energies of manganese oxide nanostructures. The spectra were
shifted with respect to the Mn 3s set at 0.0 eV2.

(2) Y. Gorlin and T. F. Jaramillo, J. Am. Chem. Soc., 2010, 132, 13612-13614.

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Figure S13. Mn 2p binding energies of manganese oxide nanostructures shows △E2p1/2. All the
spectra were calibrated to C 1s transition at 284.6 eV.

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Table S2. Caculation of electrochemically active surface areas (ECSA)

n of
n of e- per charge/ n of ECSA/ cm2 standard
entry/ sample atoms per e
coulomba coulomb electrons c
b
deviationf
cm2 d
1st α-MnO2-SF 6.24E+18 3.74E-04 2.33E+15 8.50E+14 2.74
2nd 6.24E+18 4.02E-04 2.51E+15 8.50E+14 2.95
3rd 6.24E+18 5.43E-04 3.39E+15 8.50E+14 3.99
4th 6.24E+18 4.86E-04 3.03E+15 8.50E+14 3.57
Aver. 3.31 0.57
1st
6.24E+18 3.96E-04 2.47E+15 8.50E+14 2.91
Ni/α-MnO2-SF
2nd 6.24E+18 4.55E-04 2.84E+15 8.50E+14 3.34
3rd 6.24E+18 3.09E-04 1.93E+15 8.50E+14 2.27
4th 6.24E+18 3.70E-04 2.31E+15 8.50E+14 2.72
Aver. 2.81 0.45
1stα-MnO2-HT 6.24E+18 9.56E-05 5.97E+14 8.50E+14 0.70
2nd 6.24E+18 1.56E-04 9.71E+14 8.50E+14 1.14
3rd 6.24E+18 1.61E-04 1.00E+15 8.50E+14 1.18
4th 6.24E+18 1.06E-04 6.63E+14 8.50E+14 0.78
Aver. 0.95 0.25
a. The number of electrons per coulomb, 1/e =1/1.602176487(40)×10−19 C = 6.24 E+18.
b. Integration of the charge under anodic sweep branch of CV curves.
c. The number of electrons transferred in total, calculated by dividing the charge (b) by n of
electrons per coulomb (a).
d. The number of Mn atoms per surface area (cm2) for α-MnO2.
e. Electrochemically active surface area (ECSA, cm2), equal to the total numbers of electrons (c)
divided by the atoms per surface area (d, cm2), assuming only one monolayer of Mn involved
in this oxidation process (from Mn3+ to Mn4+), thus the value of ECSA is the upper value due
to more than one single layer could be involved in this oxidation.
f. The calculation of ECSA is based on four independent trials of CV measurements (1st~4th),
hence the average number is also reported with the standard deviation.

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Figure S14. Equivalent circuit used to obtain charge transfer resistance of the OER catalysts.
Rs is the resistance of the electrolyte.
Rf is the resistance of the catalysts layer and Cf the capacitance.
Cdl is the double layer capacitance and Rct the charge transfer resistance.

Table S3. Elemental values of fitted equivalent circuit corresponding to the EIS spectra

Rs/ Ω Rf/ Ω Cf/ µF Rct/ Ω Cct/µF

α-MnO2-SF 47.8 33.0 149 91.8 1174
Ni/α-MnO2-SF 35.1 19.7 547 144.6 2618
α-MnO2-HT 33.2 21.2 608 206.2 1089
AMO 34.6 20.9 578 475.9 415
β-MnO2 31.8 11.48 214 613.2 219
δ-MnO2 40.4 318.5 271 666.1 845
PG-electrode 38.3 - - 2.5x104 7

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