新型氧化锌纳米材料在电化学检测对硝基苯酚中的应用

doi:10.7503/cjcu20160673

摘要/Abstract

摘要：

通过溶剂热法控制合成了花生形氧化锌纳米材料, 并利用扫描电子显微镜(SEM)、 X射线粉末衍射仪(XRD)和傅里叶变换红外光谱(FTIR)对材料进行了表征和分析. 循环伏安和Nyquist测试结果表明, 该材料具有良好的电化学导电性, 且对对硝基苯酚(p-NP)具有良好的选择性. 侧分脉冲伏安法(DPV)测试结果表明, 在p-NP浓度为0.8~24 μmol/L和32~80 μmol/L这2个浓度范围内, 电流强度与浓度呈线性关系, 通过3倍信噪比计算得出检测限分别为0.25和0.61 μmol/L. 该材料修饰的电极具有良好的稳定性和重现性, 用于实际样品中p-NP含量的测定显示出优良的效果.

关键词: 新型氧化锌纳米材料, 修饰电极, 电还原, 对硝基苯酚

Abstract:

A new type nanomaterial, peanut-like ZnO, was synthesized via hydrothermal method, and SEM and XRD were utilized to characterize and analyze the surface morphology and crystalline lattices of the nanomaterials. The electrochemical performance of the peanut-like ZnO was investigated by cyclic voltammetry, Nyquist and differential pulse voltammetry ulteriorly. The peanut-like ZnO modified electrode displayed excellent conductivity and had a strong electroreduction ability to detect p-nitrophenol, showing a good linear relationship within the concentration ranges of 0.8―24 μmol/L and 32―80 μmol/L, and the detection limits were calculated to be 0.25 μmol/L(3S/N). The modified electrodes were used to analyze and detect p-nitrophenol in real water samples with the recovery from 95.6% to 103.4%, and gave a satisfactorily result.

Key words: New type zinc oxide nanomaterial, Modified electrode, Electroreduction, p-Nitrophenol

中图分类号:

O657.1
O646

TrendMD:

胡海霞, 胡世荣, 董培辉, 唐元军, 洪可俊, 王松华. 新型氧化锌纳米材料在电化学检测对硝基苯酚中的应用. 高等学校化学学报, 2017, 38(7): 1171.

HU Haixia, HU Shirong, DONG Peihui, TANG Yuanjun, HONG Kejun, WANG Songhua. Synthesis of New Type ZnO Nanomaterial and Its Application for Electrochemical Detection of p-Nitrophenol^†. Chem. J. Chinese Universities, 2017, 38(7): 1171.

图/表 11

Fig.1 SEM images of ZnO(11)(A), ZnO(15)(B) and ZnO(23)(C) and high magnification SEM

Fig.2 XRD patterns(A) and FTIR spectra(B) of ZnO(11)(a), ZnO(15)(b) and ZnO(23)(c) and zeta potential of ZnO(23)(C)

Fig.3 Nyquist plots of bare GCE(a) and ZnO(23)/GCE(b) in 5 mmol/L[Fe(CN)]3-/4-+0.1 mol/L KCl(A) and CV curves of bare GCE(a) and ZnO(23)/GCE(b) in 0.1 mol/L PBS(pH=7)+20 μmol/L p-NP(B)(scan rate: 100 mV/s)

Fig.4 CV curves of ZnO(23)/GCE in 20 μmol/L p-NP and 0.01 mol/L PBS at different scan rates(A) and the relationship between peak current at about -0.8 V and square root of scan rateScan rate/(mV·s-1) from a to j: 10, 20, 40, 60, 80, 100, 120, 150, 200, 250.

Fig.5 CV curves of ZnO(23)/GCE in 20 μmol/L p-NP and 0.01 mol/L PBS at different pH values(from 4 to 9)(A) and the effect of pH on peak current at about -0.8 V(B)The inset is the plots of peak potential of p-NP vs. pH values.

Scheme 1 Schematic drawing of electrochemical sensing p-NP

Fig.6 DPV curves of different concentrations of p-NP in 0.1 mol/L PBS(pH=6)(A) and plots of peak current vs. concentration of p-NP(B)c(p-NP)/(μmol·L-1) from a to p: 0.8, 1.6, 3.2, 4.8, 6.4, 8.0, 9.6, 12, 16, 20, 24, 32, 40, 48, 64, 80.

Table 1 Characteristics of different modified electrodes

Modified electrode	Method	Linear range/(μmol·L^-1)	LOD/(μmol·L^-1)	Recovery(%)	Ref.
GO/GCE	DPV	0.1—120(R²=0.9975)	0.02	99.0—102.3	[1]
Mg(Ni)FeO/CPE^a	DPV	2—200(R²=0.9990)	0.2	96.8—100.2	[2]
OMCs^b/GCE	DPV	2.0—90(R²=0.9970)	0.1	97.2—98.8	[3]
α-CD/CRG^c/GCE	DPV	0.1—150(R²=0.9990)	0.033	96.7—102.4	[4]
rGO-Au/GCE	DPV	0.05—2.0(R²=0.9981)	0.01	98.4—104.0	[5]
CD-Au@CGS^d/GCE	DPV	0.01—200( )		97.5—105.6	[6]
ZnO/GCE	CV	10—1000(R²=0.9950)	13		[7]
GC-Co₃O₄/GCE	SWV	2—47(R²=0.9970)	0.93		[8]
ZnO/F/GCE	SWV	0.035—1.4(R²=0.9988); 2.1—6.3(R²=0.9977)	0.008	96.8—105.7	[9]
rGO-Ag/GCE	AP^e	1—10( ); 10—110( )	0.32	94.26—100.2	[10]
ZnO(23)/CHCl₃/GCE	DPV	0.8—24(R²=0.9932); 32—80(R²=0.9916)	0.25	95.6—103.4	This work

Fig.7 Stability(A) and reproducibility(B) of ZnO(23)/GCE with repetitive measurements of DPV response for 20 μmol/L p-NP in 0.1 mol/L PBS with pH=6

Fig.8 DPV of ZnO(23)/GCE in 20 μmol/L p-NP, o-NP, m-NP, and mixture of 20 μmol/L o-NP, m-NP, p-NP(0.1 mol/L PBS)

Table 2 Experimental results for determination of p-NP in water

Sample	p-NP Added/(μmol·L^-1)	p-NP Found/(μmol·L^-1)	Recovery(%)	RSD(%)
Chiu-lung river	4.8	4.62	96.3	4.4
	9.6	9.18	95.6	4.1
	20.0	20.56	102.8	3.9
Barrelled water	4.8	4.68	97.5	4.3
	9.6	9.32	97.1	3.7
	20.0	20.68	103.4	4.7

参考文献 40

[1]	Ahmad K., Mohammad A., Mathur P., Electrochimica Acta,2016, 215, 435—446
[2]	Ozay H., Sci. Adv. Mater., 2013, 5(6), 575—582
[3]	Chen D. H., Peng R. L., Zhou H., Liu H., Microchim Acta,2016, 183, 1699—1704
[4]	Manera M., Miró M., Estela J. M., Cerdà V., Segundo M. A., Lima J. L. F. C., Anal. Chim. Acta,2007, 600(1/2), 155—163
[5]	Wang S. P., Chen H. J., J. Chromatography A,2002, 979(1), 439—446
[6]	Padilla-Sánchez J. A ., Plaza-Bolaños P., Romero-González R.,Garrido-Frenich A., Martínez Vidal J. L., Journal of Chromatography A,2010, 1217(36), 5724—5731
[7]	Norwitz G., Nataro N., Keliher P. N., Anal. Chem., 1986, 58, 639—641
[8]	Guo X. F., Wang Z. H., Zhou S. P., Talanta,2004, 64(1), 135—139
[9]	Zhang W., WilsonC. R., Danielson N. D., Talanta,2008, 74(5), 1400—1407
[10]	Ahmed G. H. G., Laíño R. B., Calzón J. A. G., Microchimica Acta,2015, 182(1/2), 51—59
[11]	Hofmann D., Hartmann F., Herrmann H., Analytical and Bioanalytical Chemistry,2008, 391(1), 161—169
[12]	Wissiack R., Rosenberg E., Journal of Chromatography A,2002, 963(1), 149—157
[13]	Chen K., Zhang Z. L., Liang Y. M., Sensors,2013, 13(5), 6204—6216
[14]	Chen C., Chen H., Shi J., Science of Advanced Materials,2013, 5(7), 896—903
[15]	Mehta S. K., Singh K., Umar A., Electrochimica Acta,2012, 69, 128—133
[16]	Abaker M., Dar G. N., Umar A., Science of Advanced Materials,2012, 4(8), 893—900
[17]	Li J., Kuang D., Feng Y., J. Hazard. Mater., 2012, 201, 250—259
[18]	Chen Z. M., Zhang J. N., Guo Y. L., Chem. Res. Chinese Universities,2014, 30(4), 690—697
[19]	Fang Y., Ma L. L., Shan D. L.,LU X. Q., Chem. J. Chinese Universities,2015, 36(8), 1491—1497
	(方燕, 马琳琳, 陕多亮, 卢小泉.高等学校化学学报, 2015, 36(8), 1491—1497)
[20]	Giribabu K., Suresh R., Manigandan R., Analyst,2013, 138(19), 5811—5818
[21]	Zhang T., Lang Q., Yang D., Electrochim.Acta,2013, 106, 127—134
[22]	Niaz A., Fischer J., Barek J., Electroanalysis,2009, 21(16), 1786—1791
[23]	Sun G., Zhang L., Zhang Y., Biosensors and Bioelectronics,2015, 71, 30—36
[24]	He Y. Y., Ge J. Y., Zhao C. Z., Chem. J. Chinese Universities,2016, 37(12), 2144—2149
	(何艳艳, 葛军营, 赵常志.高等学校化学学报, 2016, 37(12), 2144—2149)
[25]	Sinhamahapatra A., Bhattacharjya D., Yu J. S., RSC Advances,2015, 5(47), 37721—37728
[26]	Bashami R. M., Hameed A., Aslam M., Analytical Methods,2015, 7(5), 1794—1801
[27]	Gong X. Y., Yu L., Tian G. H., Materials Letters,2014, 127, 36—39
[28]	Zhang G., Hou S., Zhang H., Zeng W., Yan F., Li C. C., Duan H., Advanced Materials,2015, 27, 2400—2405
[29]	Boccuzzi F., Borello E., Zecchina A., Journal of Catalysis,1978, 51(2), 150—159
[30]	Look D. C ., Claflin B., Smith H. E., Applied Physics Letters,2008, 92(12), 122108
[31]	Lu Y. F ., Ni H. Q., Mai Z. H., Journal of Applied Physics,2000, 88(1), 498—502
[32]	Zhang X., Qin J., Xue Y., Scientific Reports,2014, 4, 4596
[33]	Yin H., Ma Q., Zhou Y., Electrochimica Acta,2010, 55(23), 7102—7108
[34]	Giribabu K ., Suresh R., Manigandan R., Analyst,2013, 138(19), 5811—5818
[35]	Liu X .Y., Bulletin of the Korean Chemical Society, 2010, 31(5), 1182—1186
[36]	Chu L., Han L., Zhang X., J. Appl. Electrochem., 2011, 41, 687—694
[37]	Yin H., Zhou Y., Ai S., Liu X., Zhu L., Microchim.Acta,2010, 169, 87—92
[38]	Casella G. I., Contursi M., J. Electrochem. Soc., 2007, 154, 697—702
[39]	Ndlovu T., Arotiba O. A., Krause W. R., Mamba B. B., Int. J. Electrochem. Sci., 2010, 5, 1179—1186
[40]	Huang W., Yang C., Zhang S., Anal. Bioanal. Chem., 2003, 375, 703—707