CuO and spinel CuCo2O4 supported on mesoporous nanocubes with dual redox-active centers for electrocatalytic H2O2 reduction and sensing

The copper hexacyanoferrate (CuHCF) nanocube and its cobalt-substituted analogue (CoCuHCF) possess numerous micropores; however, they demonstrate limited electrocatalytic performance for H2O2 reduction. Heat treatment of CuHCF in air (CuHCF-ht) results in the formation of CuO and Fe3O4 with noticeable aggregation. In contrast, the heat treatment of CoCuHCF in air (CoCuHCF-ht) preserves its nanocube structure while also forming a spinel CuCo2O4 phase. The partial substitution of cobalt ions for copper ions in CuHCF enhances both thermal and structural stability, leading to the transformation of micropores into mesopores during heat treatment. This transformation improves electrolyte accessibility and structural integrity. The CoCuHCF-ht electrode features dual redox-active centers (Cu+/Cu2+ couple) derived from the CuO and CuCo2O4 phases, serving as catalytic redox mediators for H2O2 reduction. This dual redox activity results in superior performance for H2O2 reduction compared to CuHCF-ht, which only exhibits a single pair of Cu+/Cu2+ couple from CuO as an active mediator. This enhanced performance is evidenced by a lower Tafel slope, a higher catalytic rate constant, and improved mass transfer of analytes. The CoCuHCF-ht catalyst, characterized by dual redox-active centers in mesoporous nanocubes, demonstrates a high sensitivity of 234.03 mu A mM- 1 cm- 2 and a low limit of detection (0.26 mu M), along with high selectivity, stability, repeatability, and reproducibility.