电化学沉积制备纳米结构铜电极及其葡萄糖检测性能

doi:10.7503/cjcu20131049

摘要/Abstract

摘要：

利用电化学沉积法制备了高电活性的纳米结构铜电极材料, 采用扫描电子显微镜和电化学方法分别对电极表面形貌和电化学性能进行了表征, 研究了实验参数对葡萄糖电氧化活性的影响. 结果表明, 改变沉积条件可以调控沉积铜的形貌及电催化活性. 在最佳条件下制备的铜纳米结构电极对葡萄糖检测的灵敏度为1310 μA·L/mmol, 检出限为5.0×10^-7 mol/L(S/N=3).

关键词: 电沉积, 纳米结构, 铜, 电催化

Abstract:

Nanostructured copper electrode was fabricated by electrodeposition of Cu on polyelectrolyte porous film at high overpotentials in acid condition. The effects of electrodeposition parameters on the morphology of electrodeposited Cu and the glucose electrooxidation activity were investigated by scanning electron microscope and electrochemical techniques. The results revealed that well-distinct nanostructured copper electrodes were achieved by electrodeposition of Cu on polyelectrolyte porous film at high overpotentials in acid condition. Cu/PSS/PDDA/ITO electrode which is obtained under optimal conditions exhibited high sensitivity(1310 μA·L/mmol), fast response(2—3 s), wide linear range(1.0×10^-6—5.0×10^-3 mol/L) and low detection limit(5.0×10^-7 mol/L) in glucose determination at a lower overpotential of 0.40 V, with excellent resistance towards electrode fouling.

Key words: Electrodeposition, Nanostructures, Copper, Electrocatalysis

中图分类号:

O657

TrendMD:

辛华, 陈丽波, 史鸿雁, 宋文波, 刘铁梅. 电化学沉积制备纳米结构铜电极及其葡萄糖检测性能. 高等学校化学学报, 2014, 35(3): 482.

XIN Hua, CHEN Libo, SHI Hongyan, SONG Wenbo, LIU Tiemei. Electrodeposition of Nanostructured Cu Electrode and Its Glucose Assay Performance^†. Chem. J. Chinese Universities, 2014, 35(3): 482.

图/表 9

Table 1 Comparison of electrocatalytical properties towards glucose oxidation(1.0 mmol/L) at Cu/PSS/PDDA/ITO electrodes prepared by different electrodeposition methods

Electrodeposition method	Start oxidation current/V	0.45 V Oxidation current/μA
Constant current electrodeposition(I=-1.20 mA, t=10 s)	0.32	550.32
Constant potential electrodeposition(E=-1.20 V, t=10 s)	0.30	746.78
Potential step electrodeposition(E₁=-1.50 V, t₁=2 s; E₂=-1.00 V, t₂=8 s)	0.32	431.25

Fig.1 Evolution of oxidative peak current(a) at 0.40 V and onset potential(b) of 0.2 mmol/L glucose at Cu/PSS/PDDA/ITO deposited at different potentials for 10 s in 0.5 mol/L H2SO4 containing 0.1 mol/L CuSO4

Fig.2 Evolution of oxidative peak current(a) at 0.40 V and onset potential(b) of 0.2 mmol/L glucose at Cu/PSS/PDDA/ITO deposited at -1.20 V for different time in 0.5 mol/L H2SO4 containing 0.1 mol/L CuSO4

Fig.3 SEM images of PSS/PDDA/ITO(A) and Cu/PSS/PDDA/ITO(B) and CV curve of Cu/PSS/PDDA/ITO in 0.1 mol/L NaOH at 50 mV/s(C)

Fig.4 Current responses of glucose with different concentrations at Cu/PSS/PDDA/ITO electrode(A) and its calibration curve(B) (A) c(Glucose)/(mmol·L-1): a. 0; b. 0.1; c. 0.2; d. 0.3; e. 0.4.

Fig.5 Plots of oxidation current density(a) and signal-to-background ratio(b) to the applied potential at Cu/PSS/PDDA/ITO electrode obtained by chronoamperometry

Fig.6 Steady-state current-time response of Cu/PSS/PDDA/ITO electrode with successive addition of 1.0 mmol/L glucose into 0.1 mol/L NaOH at 0.40 V(A) and calibration curve for amperome-tric response to glucose at Cu/PSS/PDDA/ITO electrode(B)

Fig.7 Ampermetric current response of Cu/PSS/PDDA/ITO electrode to 1.0 mmol/L glucose and other interferences in 0.1 mol/L NaOH at +0.40 Vc(AA)=c(UA)=0.1 mmol/L; c(Ethanol)=c(OA)=10 mmol/L.

Table 2 Results of analysis of standard samples with different concentrations of glucose at 0.40 V

Sample	Glucose concentration/ (mmol·L^-1)	Detected results on Cu/PSS/PDDA/ITO/(mmol·L^-1)	Recovery(%)	Detected results by standard spectrophotometry/(mmol·L^-1)
1	0.20	0.2055	102.80	0.2025
2	0.50	0.5013	100.30	0.5026
3	0.80	0.7973	99.66	0.8019
4	1.00	0.9904	99.04	1.0350
5	2.10	2.1420	102.00	2.1020
6	3.50	3.4630	98.94	3.5080

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