We demonstrate that Co(3)O(4) nanoparticles (NPs) exhibit intrinsic peroxidase-like activity and catalase-like activity. The peroxidase-like activity of the Co(3)O(4) NPs originates from their ability of electron transfer between reducing substrates and H(2)O(2), not from ˙OH radical generated. As peroxidase mimetics, Co(3)O(4) NPs were used for colorimetric determination of H(2)O(2) and glucose.

The applications of inorganic nanomaterials as biomimetic catalysts are receiving much attention because of their high stability and low cost. In this work, Co3O4 nanomaterials including nanoplates, nanorods, and nanocubes were synthesized. The morphologies and compositions of the products were characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The catalytic properties of Co3O4 nanomaterials as catalase mimics were studied. The Co3O4 materials with different morphology exhibited different catalytic activities in the order of nanoplates > nanorods > nanocubes. The difference of the catalytic activities originated from their different abilities of electron transfer. Their catalytic activities increased significantly in the presence of calcium ion. On the basis of the stimulation by calcium ion, a biosensor was constructed by Co3O4 nanoplates for the determination of calcium ion. The biosensor had a linear relation to calcium concentrations and good measurement correlation between 0.1 and 1 mM with a detection limit of 4 μM (S/N = 3). It showed high selectivity against other metal ions and good reproducibility. The proposed method was successfully applied for the determination of calcium in a milk sample.

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The peroxidase-like activity of graphitic carbon nitride (g-C3N4) is dramatically increased by a small cobalt doping. The cobalt-doped g-C3N4 was used for wastewater treatment, exhibiting much higher degradation rate than that of pure g-C3N4.

Nanomaterials as enzyme mimics have received considerable attention as they can overcome some serious disadvantages associated with the natural enzymes. In recently developed Co3O4 nanoparticles as peroxidase mimics, the influence of the crystal plane on the catalytic performance has not been demonstrated. In order to better understand their crystal plane-dependent catalysis, the present study was initiated using three different Co3O4 nanomaterials, nanoplates, nanorods and nanocubes, as model systems. According to HRTEM, the predominantly exposed planes of nanoplates, nanorods and nanocubes are {112}, {110} and {100} planes, respectively. The catalytic activities were explored by using H2O2 and different organic substrates as the substrates of peroxidase mimics, and were investigated in-depth by steady-state kinetics and electrochemistry methods in depth. The results show that the peroxidase-like activity increases from nanocubes to nanoplates, via nanorods. The effect of external conditions such as pH and temperature on the three nanomaterials is the same, which indicates that the difference in their catalytic activities originates from their different shapes. The peroxidase-like catalytic activities of Co3O4 nanomaterials are crystal plane-dependent and follow the order: {112} ≫ {110} > {100}. The three crystal planes have different arrangements of surface atoms, thus exhibiting different abilities of electron transfer, which induce their different peroxidase-like catalytic activities. This investigation clarifies that the peroxidase-like activity of Co3O4 nanomaterials can be enhanced by shape control. These findings show that Co3O4 nanomaterials can serve as catalyst models for designing other catalysts.