New insight into electrochemical denitrification using a self-organized nanoporous V_O-Co₃O₄/Co cathode:...

A novel self-organized nanoporous V_O-Co₃O₄/Co cathode was prepared via anodization and plasma treatment and obtained a significant nitrate reduction efficiency. In the anodization, an oxide layer with the nano-sized pore structure initially grew in-situ on the Co substrate and showed a better surface area. Subsequently, He-plasma increased surface oxygen vacancies (V_O) from 24 % to 57 %. Electrons in vacancies were charged into empty e_g orbital of low-spin Co³⁺(O_h, octahedral) and firstly generated high-spin Co²⁺(O_h) with the configuration of t_2g⁶e_g¹, accounting for 71.7 % of cobalt species. Accordingly, two original mechanisms (Vo-catalyzed and Co²⁺(O_h)-catalyzed) were concluded in this study. Oxygen vacancies increased the charge intensity and served as absorption sites in nitrate reduction. Meanwhile, massive Co²⁺(O_h) provided electrons in the e_g orbital with a higher energy state and mediated the faster electron transfer through a Co²⁺-Co³⁺-Co²⁺ redox cycle, compared with Co²⁺ (T_d, tetrahedral). Ultimately, a faster reaction kinetic of 0.0220 min^-1 was achieved by V_O-Co₃O₄ than other cathodes e.g., Co₃O₄ (0.0150 min^-1). Such V_O-Co₃O₄/Co cathode-based denitrification strategy displayed great advantages in engineering application and completely removed 90 % of TN from actual wastewater.