Stable controlled growth of 3D CuO/Cu nanoflowers by surfactant-free method for non-enzymatic hydrogen peroxide detection

doi:10.1016/j.jmst.2017.11.030

Abstract

Abstract:

Sensitive, convenient and rapid detection of hydrogen peroxide (H₂O₂) is highly desirable in fields like fundamental biological research, food industries, and clinical & environmental analysis. Herein, a hierarchical porous CuO/Cu flower-like active electrode material for non-enzymatic H₂O₂ sensor was synthesized via a low-cost and one-step chemical oxidation of Cu powder in water bath without surfactants. In order to discuss the growth mechanism of the product, products with different growth time length were fabricated. The electro-catalysis of all products were first exhibited by cyclic-voltammetry, and the product under 6 h reaction shows the best result. The detailed electro-catalytic behaviors of the best product (under 6 h reaction) are characterized by cyclic-voltammetry and amperometry under alkaline conditions. The materials have high sensitivity of 103 μA mM^-1 cm^-2 (R² = 0.9979), low detection limit of 2 μmol/L and wide concentration range (from 2 μmol/L to 19.4 mmol/L). Large specific surface area and stabled nanostructure enabled good features, such as stability and sensitivity for the H₂O₂ determination.

Key words: CuO nanoparticles, Surfactant-free, Electrical properties, Sensors, H₂O₂

Ruimei Yuan, Hejun Li, Xuemin Yin, Leilei Zhang, Jinhua Lu. Stable controlled growth of 3D CuO/Cu nanoflowers by surfactant-free method for non-enzymatic hydrogen peroxide detection[J]. J. Mater. Sci. Technol., 2018, 34(9): 1692-1698.

Figures/Tables 9

Fig. 1. (a) XRD pattern and (b, c) SEM images of the product under 6 h reaction. (d) High-resolution transmission electron microscopy (HRTEM) images of the edge of the product. Inset: the selected area electron diffraction (SAEDP) pattern of the product.

Fig. 2. (a) XRD patterns of samples with different reaction time (20 min, 80 min, 3 h, 6 h and 12 h). (b)-(f) SEM images of the products with different reaction times: (b) 20 min; (c) 80 min; (d) 3 h; (e) 6 h; (f) 12 h.

Fig. 3. Time-current plots of samples under different reaction time with successive addition of H2O2 to the 0.1 mol/L NaOH solution at regular intervals. The applied potential was +0.60 V (vs. Ag/AgCl (sat’d KCl) reference) (CuO/Cu-20/GCE: 20 min, CuO/Cu-80/GCE: 80 min, CuO/Cu-3/GCE: 3 h, CuO/Cu-6/GCE: 6 h, CuO/Cu-12/GCE: 12 h).

Fig. 4. (a) CVs of GCE (in blue line), Cu/GCE in the absence (in yellow line) and in the presence (in green line) of 5 mmol/L H2O2, CuO/Cu/GCE (CuO/Cu-6 modified electrode) in the absence (in black line) and in the presence (in red line) of 5 mmol/L H2O2 in 0.1 mol/L NaOH solution. Scan rate = 20 mV/s (scanning range: -0.2-0.8 V). (b) CV plots of the CuO/Cu/GCE at scan rate of 10-140 mV/s in 0.1 mol/L NaOH solution. Inset: the plot of reduction peak current vs scan rate.

Fig. 5. (a) Time-current plot of CuO/Cu/GCE under +0.50 V, +0.55 V, +0.60 V, +0.65 V. (b) Amperometric response of the CuO/Cu/GCE with successive addition of H2O2 to the 0.1 mol/L NaOH solution at regular intervals. The applied potential was +0.60 V (vs Ag/AgCl (sat’d KCl) reference). (c) The enlarge pattern of the curve in the red rectangle in part (b). Inset: the curve of the respond time. (d) The calibration curve of the current density with different H2O2 concentrations.

Fig. 6. Anti-interference property of CuO/Cu/GCE to the stepwise addition of 1.0 mmol/L H2O2, 100 μmol/L AA, 100 μmol/L UA and 100 μmol/L L-Cys, followed by the successive addition of 1.0 mmol/L H2O2, at +0.60 V.

Table 1 Amperometric responses to interferons at +0.60 V with 1.0 mmol/L H2O2 in 0.1 mol/L NaOH solution.

Interferon	Response current (μA/cm²)	Percentage related to the response current of H₂O₂
H₂O₂ (1 mmol/L)	138.5	-
Uric acid (100 μmol/L)	8.4	6.1%
Ascorbic acid (100 μmol/L)	9.9	7.2%
l-Cysteine (100 μmol/L)	10.5	7.6%

Fig. 7. Amperometric response of the CuO/Cu/GCE to 1 mmol/L H2O2 in 0.1 mol/LNaOH at +0.60 V for 6000 s.

Fig. 8. Stability of the sensor stored at alkaline conditions for 21 days.

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