抗坏血酸在钴酞菁修饰碳糊电极上的电化学行为
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摘要
采用掺杂的方法制备了钴酞菁修饰碳糊电极(CoPc/CPE)。利用循环伏安法(CV)和交流阻抗谱(EIS)对修饰电极的电化学性能进行研究,并采用扫描电子显微镜(SEM)观察其表面形貌。运用循环伏安法(CV)、线性扫描伏安法(LSV)、计时电流法(CA)以及计时电量法(CC)研究了抗坏血酸在该修饰电极上的电化学行为并计算了电极过程的动力学参数。结果表明CoPc/CPE对抗坏血酸有明显的电催化作用,抗坏血酸在该修饰电极上的电极反应受扩散控制。计算了抗坏血酸的部分动力学参数:电荷转移系数(α=0.993),扩散系数(D=1.36×10~(-4)cm~2·s~(-1))以及电极反应速率常数(kf=1.62×10~(-2)cm·s~(-1));采用LSV测得抗坏血酸的氧化峰电流与浓度在1.00×10~(-3)(1.00×10~(-6)mol·L~(-1)范围内表现出良好的线性关系,检出限为5.00×10~(-7)mol·L~(-1)(S/N=3)。该修饰电极制备方法简单、灵敏度高、稳定性好,用于实际样品中抗坏血酸的含量分析,结果令人满意。
A cobalt phthalocyanine modified carbon paste electrode(CoPc/CPE) was prepared by doping.The electrochemical properties of the modifled electrode were characterized by cyclic vohammetry(CV) and electrochemical impedance spectroscopy(EIS),the surface morphology of the modified electrode was observed by scanning electron microscopy(SEM).The electrochemical behavior of ascorbic acid at the CoPc/CPE was investigated by cyclic voltammetry(CV),liner sweep voltammetry(LSV),chronoamperometry(CA),chronocoulometry(CC),at the same time,some kinetic parameters of ascorbic acid were determined.The results indicated that CoPc/CPE had obviously electrocatalytic activity toward ascorbic acid,and the electrode reaction of ascorbic acid exhibited a diffusion-controlled process.Some kinetic parameters such as the electron transfer coefficient(α=0.993),diffusion coefficient(D= 1.36×10~(-4)cm~2·s~(-1)) and the electrode reaction rate constant(kf=1.62×10~(-2)cm·s~(-1)) of ascorbic acid were calculated.The oxidation peak currents and concentrations of ascorbic acid had a good linear relationship in the range from 1.00×10~(-3)mol·L~(-1) to 1.00×10~(-6) mol·L~(-1) with a detection limit of 5.00×10~(-7)mol·L~(-1)(S/N=3) by liner sweep voltammetry(LSV).Furthermore,the preparation process of Co Pc/CPE is simple.And the electrode has high sensitivity and good stability,it can be applied to the quantitative determination of ascorbic acid in practical samples with satisfactory results.
A cobalt phthalocyanine modified carbon paste electrode(CoPc/CPE) was prepared by doping.The electrochemical properties of the modifled electrode were characterized by cyclic vohammetry(CV) and electrochemical impedance spectroscopy(EIS),the surface morphology of the modified electrode was observed by scanning electron microscopy(SEM).The electrochemical behavior of ascorbic acid at the CoPc/CPE was investigated by cyclic voltammetry(CV),liner sweep voltammetry(LSV),chronoamperometry(CA),chronocoulometry(CC),at the same time,some kinetic parameters of ascorbic acid were determined.The results indicated that CoPc/CPE had obviously electrocatalytic activity toward ascorbic acid,and the electrode reaction of ascorbic acid exhibited a diffusion-controlled process.Some kinetic parameters such as the electron transfer coefficient(α=0.993),diffusion coefficient(D= 1.36×10~(-4)cm~2·s~(-1)) and the electrode reaction rate constant(kf=1.62×10~(-2)cm·s~(-1)) of ascorbic acid were calculated.The oxidation peak currents and concentrations of ascorbic acid had a good linear relationship in the range from 1.00×10~(-3)mol·L~(-1) to 1.00×10~(-6) mol·L~(-1) with a detection limit of 5.00×10~(-7)mol·L~(-1)(S/N=3) by liner sweep voltammetry(LSV).Furthermore,the preparation process of Co Pc/CPE is simple.And the electrode has high sensitivity and good stability,it can be applied to the quantitative determination of ascorbic acid in practical samples with satisfactory results.
引文
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[15]赵伟利,周德璧,孙新阳,等.碳载钴酞菁催化剂的一步法制备及其在碱性条件下对氧的电催化还原[J].应用化学,2010,27(2):183-190.
[16]周云,郝二霞,何玉凤,等.壳聚糖-钴酞菁微球的制备及催化氧化异丙苯性能的研究[J].化工新型材料,2011,39(2):47-49.
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[18]Nada F A,Ahmed G,Fatma M A-G,et al.Electrochemistry and detection of dobutamine at gold nanoparticles cobalt-phthalocyanine modified carbon paste electrode[J].J Electrochem Soc,2015,162(12):B304-B311.
[19]谭学才,韦冬萍,邓光辉,等.维生素C在多壁碳纳米管/壳聚糖复合膜修饰玻碳电极上的电化学行为及测定[J].分析测试学报,2007,26(5):662-666.
[2]Maite C,Teresa C,Allission A,et al.High-affinity sodiumvitamin C co-transporters(SVCT)expression in embryonic mouse neurons[J].J Neurochem,2001,78:815-823.
[3]Njus D,Jalukar V,Zu J A,et al.Concerted proton-electron transfer between ascorbic acid and cytochrome b561[J].Am J Clin Nutr,1991,54(6):1179-1183.
[4]常竹,高亚萌,徐茂田.抗坏血酸在β-环糊精/聚苯胺修饰玻碳电极上的电化学行为[J].理化检验:化学分册,2015,51(7):966-969.
[5]中国卫生部药典委员会.中国药典第二部[M].北京:化学工业出版社,2000.
[6]王汉.荧光光谱电化学法测定维生素C[J].中国生化药物杂志,2012,33(2):129-132
[7]Garrido Frenich A,Hernandez Torres M E,Belmonte Vega A,et al.Determination of Ascorbic Acid and Carotenoide in Food Commodities by Liquid Chromatography with Spectrometry Detection[J].J Agric.Food Chem,2005,53(19):7371-7376.
[8]杨媛,冯晓元,石磊,等.高效液相色谱法同时测定水果蔬菜中L-抗坏血酸、D-异抗坏血酸、脱氢抗坏血酸及总维生素C的含量[J].分析测试学报,2015,34(8):934-938.
[9]杨金梅,覃超凤,余瑞林,等.分光光度法测定梨和苹果中维生素C的含量[J].安徽医学,2005,9(3):205-206.
[10]陈体伟,余小娜,王淑贤,等.电化学方法制备石墨烯-铁氰化镍复合物及对抗坏血酸的电催化氧化研究[J].分析试验室,2014,33(6):709-712.
[11]卫应亮,邵晨,李超,等.碳纳米管-Ti O2修饰电极伏安法测定维生素K3[J].化学研究与应用,2010,22(10):1231-1235.
[12]魏福祥,许嫔,何礼,等.抗坏血酸在石墨烯/聚苯胺复合膜修饰电极上的电化学行文[J].分析科学学报,2014,30(3):389-392.
[13]马旭莉,孙守斌,王忠德,等.碳纳米管/铁氰化镍/聚苯胺杂化膜对抗坏血酸的电催化氧化[J].新型碳材料,2013,28(1):27-32.
[14]胡荣,双雅琼,李伟,等.普鲁士蓝/多壁碳纳米管修饰电极测定维生素C[J].分析试验室,2009,28(7):61-64.
[15]赵伟利,周德璧,孙新阳,等.碳载钴酞菁催化剂的一步法制备及其在碱性条件下对氧的电催化还原[J].应用化学,2010,27(2):183-190.
[16]周云,郝二霞,何玉凤,等.壳聚糖-钴酞菁微球的制备及催化氧化异丙苯性能的研究[J].化工新型材料,2011,39(2):47-49.
[17]Huan-shun Yin,Yun-lei Zhou,Shi-yun Ai.Preparation and characteristic of cobalt-phthalocyanine modified carbon paste electrode for bisphenol A detection[J].J Electroanal Chem,2009,626(1-2):80-88.
[18]Nada F A,Ahmed G,Fatma M A-G,et al.Electrochemistry and detection of dobutamine at gold nanoparticles cobalt-phthalocyanine modified carbon paste electrode[J].J Electrochem Soc,2015,162(12):B304-B311.
[19]谭学才,韦冬萍,邓光辉,等.维生素C在多壁碳纳米管/壳聚糖复合膜修饰玻碳电极上的电化学行为及测定[J].分析测试学报,2007,26(5):662-666.