米粒状氧化铜化学修饰电极的制备及其对葡萄糖的检测
|
摘要
采用水热合成法与原位分解法相结合,在不使用软模板和强碱条件下制备得到了米粒状氧化铜(CuO)。将得到的CuO材料与Nafion溶液混合,制作成化学修饰电极(CME),开展葡萄糖的无酶检测。采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)分别对所制备的材料和电极的结构、形貌进行表征、分析。采用线性扫描伏安法、循环伏安法、安培响应和交流阻抗技术对所制备电极进行电化学性能测试。研究结果表明:所制备的CuO形貌在微观下酷似米粒,长度为0.5～1.0μm,直径为250～320 nm。当CuO修饰量为0.35 mg (电极表面积为0.22 cm2)时,修饰电极对葡萄糖具有较好的电化学检测性能。在0.0357～2.361 mmol/L浓度范围内存在良好的线性关系,其线性方程为:Ipa(mA)=?0.00187+0.05239c (mmol/L), R2=0.998。检出限为0.0647μmol/L,灵敏度为950.36μA·L/(mmol·cm2),且具有良好的选择性和可靠性。
A novel rice-like copper oxide(CuO) was synthesized without using soft template and alkali by hydrothermal and in-situ decomposition methods. This rice-like CuO material was made into the chemically modified electrode(CME) with Nafion solution for non-enzymatic glucose sensing. Structure and morphology of the prepared material and electrode were characterized by X-ray diffraction and scanning electron microscopy. Electrochemical performances of the obtained electrodes were investigated by linear sweep voltammetry, cyclic voltammetry, amperometric response, and electrochemical impedance spectroscopy. Results show that morphology of the obtained CuO particle is similar to rice grain. And its length and diameter are between 0.5-1.0 μm and 250-320 nm, respectively. The CME with 0.35 mg rice-like CuO(with 0.22 cm~2 electrode surface area) has an obvious current response for glucose with the linear range from 0.0357 to 2.361 mmol/L, the linear equation Ipa(mA)= -0.00187+0.05239 c(mmol/L)(R~2=0.998), the detection limit 0.0647 μmol/L, and the sensitivity 950.36 μA·L/(mmol·cm~2). Therefore, the prepared CuO CME shows a promise selectivity and reliability for detecting glucose.
A novel rice-like copper oxide(CuO) was synthesized without using soft template and alkali by hydrothermal and in-situ decomposition methods. This rice-like CuO material was made into the chemically modified electrode(CME) with Nafion solution for non-enzymatic glucose sensing. Structure and morphology of the prepared material and electrode were characterized by X-ray diffraction and scanning electron microscopy. Electrochemical performances of the obtained electrodes were investigated by linear sweep voltammetry, cyclic voltammetry, amperometric response, and electrochemical impedance spectroscopy. Results show that morphology of the obtained CuO particle is similar to rice grain. And its length and diameter are between 0.5-1.0 μm and 250-320 nm, respectively. The CME with 0.35 mg rice-like CuO(with 0.22 cm~2 electrode surface area) has an obvious current response for glucose with the linear range from 0.0357 to 2.361 mmol/L, the linear equation Ipa(mA)= -0.00187+0.05239 c(mmol/L)(R~2=0.998), the detection limit 0.0647 μmol/L, and the sensitivity 950.36 μA·L/(mmol·cm~2). Therefore, the prepared CuO CME shows a promise selectivity and reliability for detecting glucose.
引文
[1]LU N,SHAO C,LI X,et al.CuO/Cu2O nanofibers as electrode materials for non-enzymatic glucose sensors with improved sensitivity.RSC Adv,2014,4(59):31056-31061.
[2]ZHANG J,MA J,ZHANG S,et al.A highly sensitive nonenzymatic glucose sensor based on CuO nanoparticles decorated carbon spheres.Sens.Actuators B,2015,211(7):385-391.
[3]WANG X,GE C,CHEN K,et al.An ultrasensitive non-enzymatic glucose sensors based on controlled petal-like CuO nanostructure.Electrochim.Acta,2018,259(1):225-232.
[4]MONDAL S,MADHURI R,SHARMA P K.CuO nanostructure modified pencil graphite electrode for non-enzymatic detection of glucose.AIP Conference Proceedings,2017,1832(1):050011-1-3.
[5]CHAWLA M,SHARMA V,RANDHAWA J K.Facile one pot synthesis of CuO nanostructures and their effect on nonenzymatic glucose biosensing.Electrocatalysis,2017,8(1):27-35.
[6]GOU X,SUN S,YANG Q,et al.A very facile strategy for the synthesis of ultrathin CuO nanorods towards non-enzymatic glucose sensing.New J.Chem.,2018,42(8):6364-6369.
[7]YUAN R,LI H,YIN X,et al.3D CuO nanosheet wrapped nanofilm grown on Cu foil for high-performance non-enzymatic glucose biosensor electrode.Talanta,2017,174(20):514-520.
[8]LIU X,YANG Y,LIU R,et al.Synthesis of porous CuO microspheres assembled from(001)facet-exposed nanocrystals with excellent glucose-sensing performance.J.Alloy.Compd,2017,718(29):304-310.
[9]KHAYYAT S A,ANSARI S G,UMAR A.Glucose sensor based on copper oxide nanostructures.J.Nanosci.Nanotechno.,2014,14(5):3569-3574.
[10]MAHMOUD B G,KHAIRY M,RASHWAN F A.Self-assembly of porous copper oxide hierarchical nanostructures for selective determinations of glucose and ascorbic acid.RSC Adv.,2016,6(18):14474-14482.
[11]KHAN R,AHMAD R,RAI P.Glucose-assisted synthesis of Cu2Oshuriken-like nanostructures and their application as nonenzymatic glucose biosensors.Sens.Actuators B,2014,203(14):471-476.
[12]ALIZADEH T,MIRZAGHOLIPUR S.A Nafion-free non-enzymatic amperometric glucose sensor based on copper oxide nanoparticles-graphene nanocomposite.Sens.Actuators B,2014,198(9):438-447.
[13]XIANG C L,ZOU Y J,XIE J J,et al.Nafion-modified glassy carbon electrode for trace determination of indium.Anal.Lett.,2005,38(13):2045-2055.
[14]MEHER S K,RAO G R.Archetypal sandwich-structured CuO for high performance non-enzymatic sensing of glucose.Nanoscale,2013,5(5):2089-2099.
[15]JANA R,DEY A,DAS M,et al.Improving performance of device made up of CuO nanoparticles synthesized by hydrothermal over the reflux method.Appl.Surf.Sci.,2018,452(27):155-164.
[16]WANG D,YAN B,SONG C,et al.Synthesis of hierarchical self-assembled CuO and their structure-enhanced photocatalytic performance.J.Electro.Mater.,2018,47(1):744-750.
[17]LUO J,JIANG S S,ZHANG H Y,et al.A novel non-enzymatic glucose sensor based on Cu nanoparticle modified graphene sheets electrode.Anal.Chim.Acta,2012,709(1):47-53.
[18]LI K,FAN G L,YANG L,et al.Novel ultrasensitive non-enzymatic glucose sensors based on controlled flower-like CuO hierarchical films.Sens.Actuators B,2014,199(10):175-182.
[19]WANG X,LIU E,ZHANG X.Non-enzymatic glucose biosensor based on copper oxide-reduced graphene oxide nanocomposites synthesized from water-isopropanol solution.Electrochim.Acta,2014,130(16):253-260.
[20]ZHANG Y,LIU Y,SU L,et al.CuO nanowires based sensitive and selective non-enzymatic glucose detection.Sens.Actuators B,2014,191(2):86-93.
[21]VELMURUGAN M,KARIKALAN N,CHEN S J.Synthesis and characterizations of biscuit-like copper oxide for the non-enzymatic glucose sensor applications.Colloid Interf.Sci.,2017,493(9):349-355.
[22]SARAF M,NATARAJAN K,MOBIN S M.Non-enzymatic amperometric sensing of glucose by employing sucrose templated microspheres of copper oxide(CuO).Dalton T.,2016,45(13):5833-5840.
[23]JI X,WANG A,ZHAO Q.Direct growth of copper oxide films on Ti substrate for nonenzymatic glucose sensors.J.Nanomater.,2014,2014(2):287303-1-5.
[24]MA X G,ZHAO Q,WANG H,et al.Controlled synthesis of CuOfrom needle to flower-like particle morphologies for highly sensitive glucose detection.Int.J.Electrochem.Sci.,2017,12:8217-8226.
[25]YANG S,LI G,WANG D,et al.Synthesis of nanoneedle-like copper oxide on N-doped reduced graphene oxide:a threedimensional hybrid for nonenzymatic glucose sensor.Sens.Actuators B,2017,238(1):588-595.
[26]ZHANG X,SUN S,LüJ,et al.Nanoparticle-aggregated CuOnanoellipsoids for high-performance non-enzymatic glucose detection.J.Mater.Chem.A,2014,2(26):10073-10080.
[27]VINOTH V,SHERGILIN T D,ASIRI A M,et al.Facile synthesis of copper oxide microflowers for nonenzymatic glucose sensor applications.Mat.Sci.Semicon.Proc.,2018,82(8):31-38.
[2]ZHANG J,MA J,ZHANG S,et al.A highly sensitive nonenzymatic glucose sensor based on CuO nanoparticles decorated carbon spheres.Sens.Actuators B,2015,211(7):385-391.
[3]WANG X,GE C,CHEN K,et al.An ultrasensitive non-enzymatic glucose sensors based on controlled petal-like CuO nanostructure.Electrochim.Acta,2018,259(1):225-232.
[4]MONDAL S,MADHURI R,SHARMA P K.CuO nanostructure modified pencil graphite electrode for non-enzymatic detection of glucose.AIP Conference Proceedings,2017,1832(1):050011-1-3.
[5]CHAWLA M,SHARMA V,RANDHAWA J K.Facile one pot synthesis of CuO nanostructures and their effect on nonenzymatic glucose biosensing.Electrocatalysis,2017,8(1):27-35.
[6]GOU X,SUN S,YANG Q,et al.A very facile strategy for the synthesis of ultrathin CuO nanorods towards non-enzymatic glucose sensing.New J.Chem.,2018,42(8):6364-6369.
[7]YUAN R,LI H,YIN X,et al.3D CuO nanosheet wrapped nanofilm grown on Cu foil for high-performance non-enzymatic glucose biosensor electrode.Talanta,2017,174(20):514-520.
[8]LIU X,YANG Y,LIU R,et al.Synthesis of porous CuO microspheres assembled from(001)facet-exposed nanocrystals with excellent glucose-sensing performance.J.Alloy.Compd,2017,718(29):304-310.
[9]KHAYYAT S A,ANSARI S G,UMAR A.Glucose sensor based on copper oxide nanostructures.J.Nanosci.Nanotechno.,2014,14(5):3569-3574.
[10]MAHMOUD B G,KHAIRY M,RASHWAN F A.Self-assembly of porous copper oxide hierarchical nanostructures for selective determinations of glucose and ascorbic acid.RSC Adv.,2016,6(18):14474-14482.
[11]KHAN R,AHMAD R,RAI P.Glucose-assisted synthesis of Cu2Oshuriken-like nanostructures and their application as nonenzymatic glucose biosensors.Sens.Actuators B,2014,203(14):471-476.
[12]ALIZADEH T,MIRZAGHOLIPUR S.A Nafion-free non-enzymatic amperometric glucose sensor based on copper oxide nanoparticles-graphene nanocomposite.Sens.Actuators B,2014,198(9):438-447.
[13]XIANG C L,ZOU Y J,XIE J J,et al.Nafion-modified glassy carbon electrode for trace determination of indium.Anal.Lett.,2005,38(13):2045-2055.
[14]MEHER S K,RAO G R.Archetypal sandwich-structured CuO for high performance non-enzymatic sensing of glucose.Nanoscale,2013,5(5):2089-2099.
[15]JANA R,DEY A,DAS M,et al.Improving performance of device made up of CuO nanoparticles synthesized by hydrothermal over the reflux method.Appl.Surf.Sci.,2018,452(27):155-164.
[16]WANG D,YAN B,SONG C,et al.Synthesis of hierarchical self-assembled CuO and their structure-enhanced photocatalytic performance.J.Electro.Mater.,2018,47(1):744-750.
[17]LUO J,JIANG S S,ZHANG H Y,et al.A novel non-enzymatic glucose sensor based on Cu nanoparticle modified graphene sheets electrode.Anal.Chim.Acta,2012,709(1):47-53.
[18]LI K,FAN G L,YANG L,et al.Novel ultrasensitive non-enzymatic glucose sensors based on controlled flower-like CuO hierarchical films.Sens.Actuators B,2014,199(10):175-182.
[19]WANG X,LIU E,ZHANG X.Non-enzymatic glucose biosensor based on copper oxide-reduced graphene oxide nanocomposites synthesized from water-isopropanol solution.Electrochim.Acta,2014,130(16):253-260.
[20]ZHANG Y,LIU Y,SU L,et al.CuO nanowires based sensitive and selective non-enzymatic glucose detection.Sens.Actuators B,2014,191(2):86-93.
[21]VELMURUGAN M,KARIKALAN N,CHEN S J.Synthesis and characterizations of biscuit-like copper oxide for the non-enzymatic glucose sensor applications.Colloid Interf.Sci.,2017,493(9):349-355.
[22]SARAF M,NATARAJAN K,MOBIN S M.Non-enzymatic amperometric sensing of glucose by employing sucrose templated microspheres of copper oxide(CuO).Dalton T.,2016,45(13):5833-5840.
[23]JI X,WANG A,ZHAO Q.Direct growth of copper oxide films on Ti substrate for nonenzymatic glucose sensors.J.Nanomater.,2014,2014(2):287303-1-5.
[24]MA X G,ZHAO Q,WANG H,et al.Controlled synthesis of CuOfrom needle to flower-like particle morphologies for highly sensitive glucose detection.Int.J.Electrochem.Sci.,2017,12:8217-8226.
[25]YANG S,LI G,WANG D,et al.Synthesis of nanoneedle-like copper oxide on N-doped reduced graphene oxide:a threedimensional hybrid for nonenzymatic glucose sensor.Sens.Actuators B,2017,238(1):588-595.
[26]ZHANG X,SUN S,LüJ,et al.Nanoparticle-aggregated CuOnanoellipsoids for high-performance non-enzymatic glucose detection.J.Mater.Chem.A,2014,2(26):10073-10080.
[27]VINOTH V,SHERGILIN T D,ASIRI A M,et al.Facile synthesis of copper oxide microflowers for nonenzymatic glucose sensor applications.Mat.Sci.Semicon.Proc.,2018,82(8):31-38.