Fig. 2a exhibits the evolution of phases under different potentials. To make the results sensitive, we use transmission XRD with a short wavelength. As shown in the XRD pattern, three main diffraction peaks can be found belonging to CoO in the pristine CoO. It also shows that the intensity of the (111) plane increased due to the strong orientation as we described before. As the potential increased, new phases belonging to CoO(OH) appear, especially after 1.4 V. Under the potential of 1.7 V, the intensity still increased, which means the OER process can also result in Co oxidation. This result is well agreed with previous CV analysis. At the same time, XANES was also employed to detect the evolution of Co(Ⅱ). Agreed with previous reports, Co will exhibit a mixture valance state of (Ⅱ) and (Ⅲ) under high voltage.
Figs. 2b and
c show the XAFS result and the liner fitted results under different voltages [
28]. In the current part, we use CoO and Co
3O
4 to reveal the changes in detail. The fitted result is shown in
Fig. 2c. At high voltage, more Co(Ⅲ) appears due to the strong oxidation condition. That means, at the high voltage, Co(Ⅲ) plays the main role in catalyzing OER process. The absorption/desorption of intermediate products may occur on newly formed Co(Ⅲ) sites. As we described before, the (111) plane shows the highest Co(Ⅱ) atom density. So, it may exhibit the maximum surface oxidation. That also means using this plane to study the reaction mechanism is convincing. Moreover, it has been reported that the (111) plane is the most active index among the low-index crystal planes [
29]. Fig. S5 (Supporting information) shows the corresponding FT-EXAFS data in R space. It can be seen that under 1.6 V Co-O will suffer from a large distortion due to the phase change, which is well agreed with XANES and FE results. To further reflect the surface chemical statement of Co under different voltages, we also use X-ray photoelectron spectroscopy (XPS) to reflect the binding energy.
Figs. 2d and
e show XPS in Co 2p and O 1s region. The energy region of Co can be fitted into 781.2 eV and 780.05 eV contributed to Co(Ⅱ) and Co(Ⅲ) respectively [
42,
43]. These results compare the Co and O under different voltages. Agreed with our previous result, the surface oxidation state is much higher at high voltage. By fitting the XPS peak, we can observe that at 1.7 V surface Co(Ⅲ) increased from 20% to 30% (
Figs. 2d and
f). Then, we also make a detailed analysis of the O 1s region (
Figs. 2e and
g). Four feature peaks can be achieved belonging to lattice O (Co-O), Vacancy O, O—H, and water absorption. Compared with the pristine CoO, it is obvious that the H—O-related signal was enhanced due to the formation of CoOOH. It can be concluded that during the OER process, surface Co mainly exhibits the formation of CoOOH or hybridization Co
xO
y. This conclusion has also been confirmed by surface-sensitive soft-XAS measurement. As shown in
Figs. 2h and
i, the L-edge of Co and O-K edge can reflect the local structure changes of Co. Compared with the L
3-edge under 1.3 V, it shows a slight right shift of L-edge under 1.7 V indicating oxidation of Co. Moreover, the new absorption of O between 530 and 532 eV is attributed to transitions from the O 1s core level to the unoccupied t
2g and e
g, which reflects the existence of Co with higher valence [
44].