Moreover, the X-ray photoelectron spectroscopy (XPS), Ultraviolet photoelectron spectrometer (UPS), Raman spectra and electron spin-resonance spectroscopy (ESR) were carried out to further probe the structural information of catalysts obtained. As shown in XPS survey spectrums of Ru-NiCo
2O
4 NSs and NiCo
2O
4 NSs (Fig. S2 in Supporting information), the Ru 3p signal lays in Ru-NiCo
2O
4 NSs, while it does not appear in NiCo
2O
4 NSs, confirming Ru was introduced into NiCo
2O
4 NSs matrix successfully, which is consistent with the TEM-EDS result. The high-resolution O1s XPS spectra (
Fig. 2a) can be deconvoluted into three parts: lattice oxygen, oxygen vacancy, or hydroxyl group and absorbed oxygen from low binding energy to high binding energy in sequence [
36,
37] Compared with NiCo
2O
4 NSs, the binding energy of O 1s XPS spectra for Ru-NiCo
2O
4 NSs positively shifts ~0.2 eV, exhibiting a slight electron-deficiency O state. Furthermore, the binding energy of Ru 3p
3/2 in Ru-NiCo
2O
4 NSs is 463.7 eV (
Fig. 2b), which is located between the reference samples RuCl
3 (Ru
3+) and RuO
2 (Ru
4+), implying that the average valence state of Ru is between +3 and +4 in Ru-NiCo
2O
4 NSs [
27,
38]. Besides, there is no distinct difference between NiCo
2O
4 NSs and Ru-NiCo
2O
4 NSs concerning Co and Ni 2p XPS spectra, affirming the preservation of NiCo
2O
4 phase after Ru modification (Fig. S3 in Supporting information). In addition, the UPS was conducted to probe dynamics of electrons on the surface of the as-prepared catalysts [
39]. As shown in
Fig. 2c, the Ru-NiCo
2O
4 NSs and NiCo
2O
4 NSs exhibit different secondary electron cutoff energy with 16.34 eV for Ru-NiCo
2O
4 NSs and 16.22 eV for NiCo
2O
4 NSs and thus the corresponding work function are 4.88 eV and 5.00 eV for Ru-NiCo
2O
4 NSs and NiCo
2O
4 NSs, respectively. The smaller work function indicates that Ru modulation facilitates the electronic properties of Ru-NiCo
2O
4 NSs, which is contributed to enhancing catalytic activity [
40]. Besides, Raman as a surface-sensitive spectrum technology was further applied to gain insights into NiCo
2O
4 NSs before and after Ru modification. As shown in
Fig. 2d, the Ru-NiCo
2O
4 NSs showcases similar spectra patterns with the pristine NiCo
2O
4 NSs except for a slight blue shift, which is due to the doping of Ru. Furthermore, the Raman spectra of Ru-NiCo
2O
4 NSs exhibit different spectra feature compared with RuO
2 (Fig. S4 in Supporting information), which implies the Ru may exist as a highly dispersed state in NiCo
2O
4 NSs substrate and further indicating that Ru are doped into NiCo
2O
4 NSs successfully. Moreover, ESR spectra were conducted to investigate the change of oxygen vacancy. From
Fig. 2e, it can be seen that Ru-NiCo
2O
4 NSs owns a stronger ESR signal originating from the electron trapped at oxygen vacancies than that of NiCo
2O
4 counterpart [
41,
42]. Therefore, we can deduce that the Ru-NiCo
2O
4 NSs possess more oxygen vacancies than NiCo
2O
4 NSs, which is helpful to facilitate water dissociation [
43]. Furthermore, the excellent hydrophilicity feature of Ru-NiCo
2O
4 NSs supported on CFC enables the easy accessibility of reactants and fast release of product molecules, thus accelerating catalytic process (
Fig. 2f, the inset shows the contact angle of bare CFC) [
44].