Insight into the Effect of P on Co3O4/NiO Heterostructure for

Efficient Alkaline Oxygen Evolution Reaction

Xu Yu1, Xinyu Wang1, Shuang Wu, Jianliang Bai, Pinyi He, Fu Qin, Yongkang Yao, Lili Ren*

School of Chemistry & Chemical Engineering, Southeast University, Nanjing 211189, China.

* Corresponding author. E-mail address: liliren@seu.edu.cn (L. Ren).

1
These authors contributed equally to this work.
Fig. S1. XRD patterns of (a) P-Co3O4/NiO at different temperature, (b) Co 3O4/NiO,
(c) Co3O4 and (d) NiO.
Fig. S2. SEM images of (a, b) Co3O4, (c, d) NiO, (e, f) Co3O4/NiO.
Fig. S3. SEM images and the corresponding size distribution of catalysts at different
phosphating temperatures for (a, b, c) 300 ℃, (d, e, f) 350 ℃, (g, h, i) 450 ℃.
Fig. S4. EDS results of P-Co3O4/NiO.
Fig. S5. (a) XPS pattern of P-Co3O4/NiO, and Co3O4/NiO (b) P 2p High-resolution
XPS survey spectra of P-Co3O4/NiO.
Fig. S6. CV curves of catalytic electrodes at different scanning rates (20, 40, 60, 80
and 100 mV·s-1) were studied to estimate the specific surface area (C dl) of OER
electrochemical activity. (a, b), (c, d), (e, f) correspond to the catalysts P-Co 3O4/NiO
obtained at phosphating temperatures of 300 ℃, 350 ℃,400℃ and 450 ℃
respectively.
Fig. S7. Electrochemical active surface area (ECSA) of P-Co3O4/NiO catalysts
synthesized at different temperatures.

We have calculated the ECSAs of four catalysts based on formula (1).

C dl ( catalyst) × S (1)
ECSA=
C dl (fs)

Where S represents the geometric area of the working electrode (0.07065 cm 2), Cdl(fs)
represents the capacitance value of glassy carbon electrode, which is similar with that
of a flat surface (0.04 mF·cm-2) [1,2].

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Fig. S8. (a) LSV curves of Co3O4/NiO, Co3O4, NiO and glassy carbon electrode. (b)
The corresponding comparison of the overpotentials at 10 mA·cm -2 current density.
(c) Tafel plots.
Fig. S9. CV curves of catalytic electrodes at different scanning rates (20, 40, 60, 80
and 100 mV·s-1) were studied to estimate the specific surface area (C dl) of OER
electrochemical activity. (a, b) P-Co3O4/NiO, (c, d) P-Co3O4+NiO, (e, f) Co3O4/NiO,
(g, h) Co3O4 + NiO.
Fig. S10. Polarization curves after ECSA normalization for OER.
Fig. S11. Multistep chronopotentiometry curves of P-Co3O4/NiO at different current
densities.
Fig. S12. (a) (b) TEM images, (c) HRTEM image and (d) the corresponding elemental

mapping image of P-Co3O4/NiO electrocatalyst after OER test.

Fig. S13. SEM and TEM after stability test.
Table S1. The atomic ratio and weight from EDS in the P-Co3O4/NiO.

Element Atom (%) Weight (%)

OK 38.1 13.8
PK 7.6 6.2
Co K 39.2 60.4
Ni K 15.1 19.6
Total 100 100
 Table S2. Normalized Chemical compositions about Co 2p of P-Co3O4/NiO and

Co3O4/NiO electrocatalysts respectively obtained from XPS analyses.

Samples Coᵟ+ 2p3/2 Co3+ 2p3/2 Co2+ 2p3/2 Coᵟ+ 2p1/2 Co3+ 2p1/2 Co2+ 2p1/2

(wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt.%)

P-Co3O4/NiO 0.16 0.37 0.20 0.05 0.13 0.08

Co3O4/NiO 0 0.28 0.42 0 0.15 0.14

Table S3. Normalized Chemical compositions about Ni 2p of P-Co3O4/NiO and

Co3O4/NiO electrocatalysts respectively obtained from XPS analyses.

Samples Ni3+ 2p3/2 Ni 2+ 2p3/2 Ni 3+ 2p1/2 (wt. Ni 2+ 2p1/2

(wt. %) (wt. %) %) (wt. %)

P-Co3O4/NiO 0.21 0.46 0.12 0.21

Co3O4/NiO 0.16 0.49 0.11 0.24

Table S4. Normalized Chemical compositions about O 1s of P-Co3O4/NiO and

Co3O4/NiO electrocatalysts obtained respectively from XPS analyses.

Samples lattice defective oxygen absorbed oxygen (wt.

oxygen (wt. %) %)

(wt. %)

P-Co3O4/NiO 0.12 0.71 0.17

Co3O4/NiO 0.62 0.33 0.05

Table S5. Oxygen production during Faraday efficiency (FE) test

Time/min Vmeasured/mL Vcalculated/mL FE/%

0-10 0.73 0.76 96.05

10-20 0.75 0.76 98.68

20-30 0.73 0.76 96.05

30-40 0.75 0.76 98.68

40-50 0.75 0.76 98.68

50-50 0.75 0.76 98.68

Table S6. Comparison of OER catalytic performance of P-Co 3O4/NiO with recent the
most concerned electrocatalysts in 1.0 M KOH.

Catalyst Overpotential References

(η10)/mV
P-Co3O4/NiO 283 This work
Co2P 364 [1]
CoFeZn-PBA 343 [2]
P-NiCo2O4 370 [3]
Ag-CeO2-Co3O4/C 340 [4]
MnFeCoO4/Mn2S2(CO)7 310 [5]
B-Co3O4@ZIF-67 334 [6]
Ni1.5Co1.5P/MF 314 [7]
Co/CoOx@NC 307 [8]
RuO2/Co3O4 302 [9]
Co3O4/CoOxPy 295 [10]
P/Co3O4 314 [11]
CoNPs@CNT 380 [12]
Ni9Fe1-BDC-0.15CB 290 [13]
NiOx/NiCo2O4/Co3O4 315 [14]
Co2P/Ni2P 310 [15]
Ce0.21@Co(OH)2 300 [16]
Co/MoC@N-C 290 [17]
Co2P/CoP@NPGC 340 [18]
CoP-HNTs@NCL 350 [19]
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