铜纳米粒子/聚丙烯酸/石墨烯纳米复合材料修饰玻碳电极检测水中的4-硝基苯酚
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摘要
采用一种温和且简单的原位生长法将铜纳米粒子和石墨烯非共价键合,得到铜纳米粒子/聚丙烯酸/石墨烯(Cu NPs/PAA/GR)纳米复合材料,对4-硝基苯酚(4-NP)表现出良好的电催化活性。用扫描电镜对此纳米复合材料的形貌进行了表征。以此材料修饰的玻碳电极受吸附控制,4-NP在该电极表面的反应机理为两电子转移过程,电子转移数n=2.3,修饰电极的有效面积为0.6275 cm2,是裸电极的2.22倍,电极吸附量Гs为1.6×10!11mol/cm2,催化速率常数kcat的平均值为1.15×104L/(mol/s)。修饰电极的响应电流与4-NP的浓度在1~150μmol/L范围内呈良好的线性关系,线性方程为:Ipa(μA)=!0.015C(μmol/L)-0.98,(R2=0.9951),检出限为0.23μmol/L(S/N=3)。此传感器制备简单、灵敏性高、稳定性和重现性好。使用此传感器检测实际水样中4-NP的回收率为88.6%~100.7%,相对标准偏差为2.6%~5.9%。
A moderate and simple in situ growth approach was employed to load copper nanoparticles(Cu NPs) noncovalently on graphene for preparation of Cu NPs/poly acrylic acid/reduced graphene oxide(Cu NPs/PAA/GR) nanocomposites for electro-catalysis of 4-nitrophenol(4-NP).The morphology of the material was observed by scanning electron microscopy(SEM).Tests with various scan rates and p H conditions indicated an adsorption-controlled electrode process occurred.The mechanism of the electrode reaction of 4-NP involved a two-electron process accompanied by a deprotonation step.Electrochemical parameters were calculated with the electron transfer number(n) as 2.3,the effective area(0.6275 cm2) of Cu NPs/PAA/GR/GCE electrode was 2.22 times as large as that of bare electrode,the adsorption capacity Гs value was 1.6 ×10!11mol/cm2,and the average value of the calculated kcatvalue was 1.15 ×104L/(mol·s).Under the optimal conditions,the differential pulse voltammetric response of the electrode showed a linear relationship with 4-NP concentration in the range of 1-150 μmol/L.The regression equation was Ipa(μA) =!0.015C(μmol/L)-0.98(R2= 0.9951),and the detection limit was 0.23 μmol/L(S/N = 3).The fabricated sensor exhibited high sensitivity,good stability and high reproducibility.This sensor was applied for detection of 4-NP in water samples with favorable recoveries of 88.6%-100.7% and relative standard deviation(RSD) of 2.6%-5.9%.
A moderate and simple in situ growth approach was employed to load copper nanoparticles(Cu NPs) noncovalently on graphene for preparation of Cu NPs/poly acrylic acid/reduced graphene oxide(Cu NPs/PAA/GR) nanocomposites for electro-catalysis of 4-nitrophenol(4-NP).The morphology of the material was observed by scanning electron microscopy(SEM).Tests with various scan rates and p H conditions indicated an adsorption-controlled electrode process occurred.The mechanism of the electrode reaction of 4-NP involved a two-electron process accompanied by a deprotonation step.Electrochemical parameters were calculated with the electron transfer number(n) as 2.3,the effective area(0.6275 cm2) of Cu NPs/PAA/GR/GCE electrode was 2.22 times as large as that of bare electrode,the adsorption capacity Гs value was 1.6 ×10!11mol/cm2,and the average value of the calculated kcatvalue was 1.15 ×104L/(mol·s).Under the optimal conditions,the differential pulse voltammetric response of the electrode showed a linear relationship with 4-NP concentration in the range of 1-150 μmol/L.The regression equation was Ipa(μA) =!0.015C(μmol/L)-0.98(R2= 0.9951),and the detection limit was 0.23 μmol/L(S/N = 3).The fabricated sensor exhibited high sensitivity,good stability and high reproducibility.This sensor was applied for detection of 4-NP in water samples with favorable recoveries of 88.6%-100.7% and relative standard deviation(RSD) of 2.6%-5.9%.
引文
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25 Hang L F,Zhao Y,Zhang H H,Liu G Q,Cai W P,Li Y,Qu L T.Acta Mater.,2016,105:59-67
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27 Krishna R,Fernandes D M,Ventura J,Freire C,Elby T.Int.J.Hydrogen Energy,2016,41(27):11608-11615
28 Chen C M,Yang Q H,Yang Y G,Lv W,Wen Y F,Hou P X,Wang M Z,Cheng H M.Adv.Mater.,2009,21(29):3007-3011
29 Qiang X L,Xia J F,Wang Z H,Xia Y Z,Zhang F F,Li Y H.Adv.Mater.Res.,2012,600:238-241
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31 Laviron E.J.Electroanal.Chem.,1979,101(1):19-28
32 Anson F C.Anal.Chem.,1964,36(4):932-934
33 Andrieux C P,Saveant J M.J.Electroanal.Chem.,1978,93(2):163-168
34 Yin H S,Zhou Y L,Ai S Y,Liu X G,Zhu L S,Lu L N.Microchim.Acta,2010,169(1-2):87-92
35 Lupu S,Lete C,Marin M,Totir N,Balaure P C.Electrochim.Acta,2009,54(7):1932-1938
36 Chu L,Han L,Zhang X L.J.Appl.Electrochem.,2011,41:687-694
2 Zhang B,Li Feng,Wu Tao,Sun D J,Li Y J.Colloids Surf.A,2015,464:78-88
3 ZHA Fei,YU Xia,ZHU Yu,ZHENG Hai-Rong,WANG Ya-Fei.Journal of Northwest Normal University(Natural Science),2016,2:60-67查飞,于霞,朱钰,郑海蓉,王亚飞.西北师范大学学报(自然科学版),2016,2:60-67
4 Buikema A L,McG inniss M J,Cairns J.Mar.Environ.Res.,1979,2(2):87-181
5 Feng X,Gao W W,Zhou S H,Shi H Y,Huang H,Song W B.Anal.Chim.Acta,2013,805:36-44
6 EPA 822-S-12-001,2012 Edition of the Drinking Water Standards and Health Advisories
7 QIN Cheng-Hua,WANG Jing-Jing,ZHANG Jun,PENG Hua,WANG Ling-Ling,NAN Shu-Qing,LI Hong-Liang,WU LiYe.Environmental Monitoring in China,2015,04:86-90秦承华,王晶晶,张军,彭华,王玲玲,南淑清,李红亮,吴立业.中国环境监测,2015,04:86-90
8 Xin H S,Zhang Q M,Zhou Y L,Ma Q,liu T,Zhu L S,Ai S Y.Electrochim.Acta,2011,56(6):2748-2753
9 GB 5749-2006,Standards for Drinking Water Quality.National Standards of the Peoples Republic of China.生活饮用水卫生标准.中华人民共和国国家标准.GB 5749-2006
10 He K Y,Wang X S,Meng X H,Zheng H T,Suye S I.Sens.Actuators,B,2014,193:212-219
11 Gao W H,Legido-Quigley C.J.Chromatogr.A,2011,1218(28):4307-4311
12 Niu X L,Yang W,Wang G Y,Ren J,Guo H,Gao J Z.Electrochim.Acta,2013,98:167-175
13 HE Feng-Yun,PAN Zhao-Rui,ZHOU Hong,LIU Huan,YU Jing,GU Xiao-Yan,TANG Peng-Peng.Chinese J.Appl.Chem.,2015,32(2):225-231何凤云,潘兆瑞,周宏,刘欢,俞静,顾小燕,唐鹏鹏.应用化学,2015,32(2):225-231
14 Xue C,Han Q,Wang Y,Wu J H,Wen T T,Wang R Y,Hong J L,Zhou X M,Jiang H J.Biosens.Bioelectron.,2013,49:199-203
15 Saha S,Pal A,Kundu S,Basu S,Pal T.Langmuir,2010,26(4):2885-2893
16 Pradhan N,Pal A,Pal T.Langmuir,2001,17(5):1800-1802
17 Novoselov K S,Geim A K,Morozov S V,Jiang D,Zhang Y,Dubonos S V,Grigorieva I V,Firsov A A.Science,2004,306:666-669
18 ZHU Xu,LI Chun-Lan,LIU Qin,ZHU Xiao-Hua,ZHANG Yin-Tang,XU Mao-Tian.Chinese J.Anal.Chem.,2011,39(12):1846-1851朱旭,李春兰,刘琴,朱效华,张银堂,徐茂田.分析化学,2011,39(12):1846-1851
19 Li Y Z,Cao Y L,Xie J,Jia D Z,Qin H Y,Liang Z T.Catal.Commun.,2015,58:21-25
20 Zhang M M,Lu X,Wang H Y,Liu X L,Qin Y J,Zhang P,Guo Z X.RSC Adv.,2016,6(42):35945-35951
21 Wang Z M,Xu C L,Gao G Q,Li X.RSC Adv.,2014,4(26):13644-13651
22 Ye W C,Yu J,Zhou Y X,Gao D Q,Wang D A,Wang C M,Xue D S.Appl.Catal.B,2016,181:371-378
23 ZHANG Cui-Zhong,WANG Li-Wei,LU Yong-Ke,ZHENG Guang-Jin,PENG Jin-Yun.Chinese J.Anal.Chem.,2016,44(8):1263-1269张翠忠,王丽伟,卢永课,郑广进,彭金云.分析化学,2016,44(8):1263-1269
24 Guo X N,Hao C H,Jin G Q,Zhu H Y,Guo X Y.Angew.Chem.Int.Ed.,2014,53(7):1973-1977
25 Hang L F,Zhao Y,Zhang H H,Liu G Q,Cai W P,Li Y,Qu L T.Acta Mater.,2016,105:59-67
26 Shaabani A,Hezarkhani Z,Nejad M K.RSC Adv.,2016,6(36):30247-30257
27 Krishna R,Fernandes D M,Ventura J,Freire C,Elby T.Int.J.Hydrogen Energy,2016,41(27):11608-11615
28 Chen C M,Yang Q H,Yang Y G,Lv W,Wen Y F,Hou P X,Wang M Z,Cheng H M.Adv.Mater.,2009,21(29):3007-3011
29 Qiang X L,Xia J F,Wang Z H,Xia Y Z,Zhang F F,Li Y H.Adv.Mater.Res.,2012,600:238-241
30 WANG Wei-Ni,GUO Xin-Li,ZHANG Ling-Min,HAO Wei,YU Jin,SUN Li-Tao.Journal of Functional Materials,2015,16:16090-16094,16105王蔚妮,郭新立,张灵敏,郝威,于金,孙立涛.功能材料,2015,16:16090-16094,16105
31 Laviron E.J.Electroanal.Chem.,1979,101(1):19-28
32 Anson F C.Anal.Chem.,1964,36(4):932-934
33 Andrieux C P,Saveant J M.J.Electroanal.Chem.,1978,93(2):163-168
34 Yin H S,Zhou Y L,Ai S Y,Liu X G,Zhu L S,Lu L N.Microchim.Acta,2010,169(1-2):87-92
35 Lupu S,Lete C,Marin M,Totir N,Balaure P C.Electrochim.Acta,2009,54(7):1932-1938
36 Chu L,Han L,Zhang X L.J.Appl.Electrochem.,2011,41:687-694