氧化镍/镍/碳微球原位制备及葡萄糖传感性能

doi:10.15541/jim20160306

摘要/Abstract

摘要：

以葡萄糖、六水合氯化镍和尿素为原料, 通过水热反应一步制备前驱体Ni(OH)₂/C, 在高纯度氮气中煅烧获得NiO/Ni/C微球三元复合材料。采用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、X射线光谱(EDS)和拉曼(Raman)等手段, 分析NiO/Ni/C微球三元复合材料的形貌结构以及物相组成。结果表明: NiO/Ni/C微球为珊瑚花状结构, 直径约1.7 μm, Ni、NiO呈立方相。通过循环伏安法和计时电流法研究了NiO/Ni/C微球三元复合材料的电化学行为及葡萄糖传感性能。当Ni/NiO摩尔比为0.19时, 形成的NiO/Ni/C三元复合微球具有优异的葡萄糖传感性能, 其灵敏度为241.09 μA·mmol/(L·cm²), 线性响应范围为10 μmol/L~5.05 mmol/L, 最低检测限位10 μmol/L。该传感器具有灵敏度高、抗干扰能力强以及稳定性好等特点。

关键词: 微球, 三元复合材料, 葡萄糖, 电化学传感

Abstract:

Ternary NiO/Ni/C microspheres was obtained by calcination of the precursor Ni(OH)₂/C in pure nitrogen. The precursor was prepared via an one-pot hydrothermal synthesis technology using glucose, nickel chloride and urea. Scanning electron microscope (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray energy dispersive (EDS), and Raman were used to characterize the morphology and structure of the sample. Results show that the NiO/Ni/C microspheres have a coral-like structure with diameter of about 1.7 μm, and the crystalline phase of Ni and NiO are cubic. Electrochemical behavior and sensing property of ternary NiO/Ni/C microspheres composites were studied via cyclic voltammetry and amperometric method. When the Ni/NiO molar ratio is 0.19, the ternary NiO/Ni/C microspheres have excellent glucose sensor performance with a sensitivity of 241.09 μA·mmol/(L·cm²) in a range of 10-5.05 mmol/L, and a detecting limit of 10 μmol/L. Furthermore, the sensor has good stability and anti-interference ability.

Key words: microspheres, ternary composites, glucose, electrochemical sensor

中图分类号:

TQ174

秦冬昱, 何晓龙, 聂秋林, 殷好勇, 袁求理. 氧化镍/镍/碳微球原位制备及葡萄糖传感性能[J]. 无机材料学报, 2017, 32(3): 313-318.

QIN Dong-Yu, HE Xiao-Long, NIE Qiu-Lin, YIN Hao-Yong, YUAN Qiu-Li. In Situ Preparation and Glucose Sensing Property of Ternary
NiO/Ni/C Microspheres[J]. Journal of Inorganic Materials, 2017, 32(3): 313-318.

图/表 10

图1 NiO/C(a)、NiO/Ni/C-1(b)、NiO/Ni/C-2(c)和NiO/Ni/C-3 (d)的XRD图谱

Fig. 1 XRD patterns of NiO/C(a), NiO/Ni/C-1(b), NiO/ Ni/ C-2(c), and NiO/Ni/C-3(d)

图2 NiO/Ni/C-2样品的Raman光谱图

Fig. 2 Raman spectrum of NiO/Ni/C-2 sample

图3 样品NiO/C (a)、NiO/Ni/C-1 (b)、NiO/Ni/C-2 (c) 和NiO/Ni/C-3(d)的SEM照片, NiO/Ni/C-2的高倍SEM照片(e) 以及NiO/Ni/C-2 的EDS能谱图(f)

Fig. 3 SEM images of NiO/C (a), NiO/Ni/C-1 (b), NiO/Ni/C-2 (c), and NiO/Ni/C-3 (d), as well as enlarged image of NiO/Ni/C-2 (e), and its EDS pattern of NiO/Ni/C-2 (f)

图4 NiO/Ni/C-2样品的TEM照片和HRTEM照片

Fig. 4 TEM (a) and HRTEM(b) images of NiO/Ni/C-2

图5 不同样品在1mmol/L葡萄糖溶液中的CV曲线

Fig. 5 CV curves of different samples at 1 mmol/L glucose solution

图6 不同样品的电化学阻抗谱

Fig. 6 EIS spectra of different samples

图7 NiO/Ni/C-2/GCE 在不同浓度葡萄糖溶液中以扫描速率为50 mV/s的CV曲线

Fig. 7 CV of NiO/Ni/C-2/GCE in glucose solution with different concentrations at scan rate of 50 mV/s

图8 样品NiO/C(a)、NiO/Ni/C-1(b)、NiO/Ni/C-2(c)和 NiO/Ni/C-3(d)葡萄糖传感器的i-t曲线

Fig. 8 i-t curves of NiO/C (a) ,NiO/Ni/C-1 (b), NiO/Ni/C-2 (c) and NiO/Ni/C-3 (d) glucose sensorsInset shows linear calibration of NiO/Ni/C-2 sensors between current response and glucose concentration

图9 NiO/Ni/C-2 葡萄糖传感器的干扰测试

Fig. 9 Interference test of NiO/Ni/C-2 glcose sensor

表1 葡萄糖回收率的测定值

Table 1 Determination of glucose recovery

Spiked/(mmol·L^-1)	Found/(mmol·L^-1)	Recovery/%
0.21	0.20	95.0
0.41	0.42	104.8
0.61	0.63	109.5
0.81	0.82	104.7

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