Determination of Hydrogen Peroxide by Cyclic Voltammetry Based on Nano TiO2 and TiN as Working Electrode
摘 要
制备了纳米TiO2、TiN材料,将其作为工作电极,建立了循环伏安法测定过氧化氢含量的方法。将钛片置于含10.0 g氟化铵、0.6 g脲、24 mL 30%(质量分数)过氧化氢溶液、24 mL硝酸组成的抛光液中进行下表面抛光处理,再加入15 mL丙酮、15 mL无水乙醇、15 mL水,超声处理15 min后,得到光亮钛片。以光亮钛片为阳极,普通钛片为阴极,在不同电解质[TiO2粗糙膜对应的电解质为1.0 mol·L-1硫酸溶液;TiO2纳米管为50 mL丙三醇、50 mL水、0.2 mol·L-1硫酸溶液、0.5%(质量分数)氟化钠溶液;TiO2纳米孔为100 mL乙二醇、1 mL水、0.38%(质量分数)氟化铵溶液]中,采用阳极氧化法,得到不同形貌大小的TiO2粗糙膜、TiO2纳米管、TiO2纳米孔;再通过氨气热还原,得到TiN粗糙膜、TiN纳米管、TiN纳米孔。以TiO2和TiN材料为工作电极,铂片为辅助电极,Ag/AgCl为参比电极,将三电极体系置于磷酸盐缓冲溶液(pH 7.0)中,采用循环伏安法法测定过氧化氢含量。结果显示:TiN粗糙膜、TiN纳米管、TiN纳米孔电极的速率常数分别为2.39×10-6,3.03×10-6,6.40×10-6cm·s-1;以TiO2粗糙膜、TiN粗糙膜、TiO2纳米管、TiN纳米管、TiO2纳米孔、TiN纳米孔为工作电极,过氧化氢的浓度在一定范围内与其对应的还原峰电流呈线性关系,检出限(3s/k)分别为23.30,14.29,19.9,10.6,16.9,5.02 μmol·L-1;在磷酸盐缓冲溶液(pH 7.0)中滴加50 μmol·L-1 H2O2溶液,采用计时电流法在-0.4 V外加电压下进行测定,计算得TiN粗糙膜、TiN纳米管、TiN纳米孔响应电流的相对标准偏差(RSD,n=5)分别为4.7%,3.2%和7.3%。
Abstract
A method for determination of H2O2 by cyclic voltammetry using nano TiO2 and TiN materials as working electrode was established. The lower surface of Ti sheet was polished in polishing solution including 10.0 g of ammonium fluoride, 0.6 g of urea, 24 mL of 30% (mass fraction) hydrogen peroxide solution and 24 mL of nitric acid, and treated with ultrasonic for 15 min in a mixture of 15 mL of acetone, 15 mL of anhydrous ethanol and 15 mL of water. Then bright Ti sheet obtained was used as anode, and ordinary Ti sheet was used as cathode. TiO2 rough film, TiO2 nanotube and TiO2 nanopore with different morphologies were prepared in different electrolytes[1.0 mol·L-1 sulfuric acid solution for TiO2 rough film; a mixture of 50 mL of glycerin, 50 mL of water, 0.2 mol·L-1 sulfuric acid solution and 0.5% (mass fraction) sodium fluoride solution for TiO2 nanotube; a mixture of 100 mL of glycol, 1 mL of water and 0.38% (mass fraction) ammonium fluoride solution for TiO2 nanopore] by anodic oxidation method, and TiN rough film, TiN nanotube and TiN nanopore were obtained by ammonia thermal reduction reaction. TiO2 and TiN materials were used as working electrode, platinum sheet as auxiliary electrode, and Ag/AgCl as reference electrode, and H2O2 was determined by cyclic voltammetry with three electrodes system in phosphate buffer solution (pH 7.0). It was showed that the rate constants of TiN rough film, TiN nanotube and TiN nanopore electrode were 2.39×10-6, 3.03×10-6cm·s-1 and 6.40×10-6 cm·s-1, respectively. Using TiO2 rough film, TiN rough film, TiO2 nanotube, TiN nanotube, TiO2 nanopore and TiN nanopore as working electrodes, linear relationships between concentrations of hydrogen peroxide and their reduction peak currents were kept in definite ranges, with detection limits (3s/k) of 23.30, 14.29, 19.9, 10.60, 16.90, 5.02 μmol·L-1. 50 μmol·L-1 H2O2 solution dropped in phosphate buffer solution (pH 7.0) was determined by chronoamperometry at -0.4 V of externaly applied voltage, and RSDs (n=5) of response currents of TiN rough film, TiN nanotube and TiN nanopore were 4.7%, 3.2% and 7.3%, respectively.
中图分类号 O657.1 TQ123.6 DOI 10.11973/lhjy-hx202201006
所属栏目 工作简报
基金项目 浙江省自然科学基金(No.LY18B050006);国家重点研究开发计划(No.3027YFB0307503)
收稿日期 2020/6/30
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备注黄章烤,硕士,主要从事应用电化学工作
引用该论文: HUANG Zhangkao,WANG Linling,ZHAO Fengming. Determination of Hydrogen Peroxide by Cyclic Voltammetry Based on Nano TiO2 and TiN as Working Electrode[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2022, 58(1): 32~39
黄章烤,王琳玲,赵峰鸣. 基于纳米TiO2和TiN为工作电极的循环伏安法测定过氧化氢的含量[J]. 理化检验-化学分册, 2022, 58(1): 32~39
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【2】PEI Y J, HU M, TANG X Y, et al. Ultrafast one-pot anodic preparation of Co3O4/nanoporous gold composite electrode as an efficient nonenzymatic amperometric sensor for glucose and hydrogen peroxide[J]. Analytica Chimica Acta, 2019,1059:49-58.
【3】XIE Z, LIU X, WANG W, et al. Fabrication of TiN nanostructure as a hydrogen peroxide sensor by oblique angle deposition[J]. Nanoscale Research Letters, 2014,9(1):105.
【4】DONG Y Z, WU Y M, LIU M J, et al. Electrocatalysis on shape-controlled titanium nitride nanocrystals for the oxygen reduction reaction[J]. ChemSusChem, 2013,6(10):2016-2021.
【5】于仁红,蒋明学.TiN的性质、用途及其粉末制备技术[J].耐火材料, 2005,39(5):386-389.
【6】徐红霞,王在伟,张传健,等.CoSe/TiN同轴纳米管阵列在染料敏化太阳能电池对电极中的应用研究[J].影像科学与光化学, 2017,35(5):758-764.
【7】姜俊峰,徐海波,王廷勇,等.TiN基IrO2+Ta2O5涂层电催化性能研究[J].稀有金属材料与工程, 2007,36(2):344-348.
【8】赵峰鸣,闻刚,孔丽瑶,等.氮化钛纳米管作为钒电池负极对Ⅴ(Ⅱ)/Ⅴ(Ⅲ)的电化学性能[J].无机化学学报, 2017,33(3):501-508.
【9】ANNALAKSHMI M, BALASUBRAMANIAN P, CHEN S M, et al. Amperometric sensing of nitrite at nanomolar concentrations by using carboxylated multiwalled carbon nanotubes modified with titanium nitride nanoparticles[J]. Mikrochimica Acta, 2018,186(1):8.
【10】孙凤久,于撼江,张军.在大气气氛下应用激光和等离子体混合方法制备氮化钛[J].中国激光, 2008,35(1):125-130.
【11】孙金峰,李晓普,梁宝岩,等.反应球磨钛与尿素制备氮化钛的反应机理研究[J].无机材料学报, 2009,24(4):759-763.
【12】魏颖娜,卜景龙,魏恒勇,等.PVP对碳热还原氮化法制备TiN薄膜的影响[J].人工晶体学报, 2015,44(7):1838-1842.
【13】江涛,马敏庄.氮化钛的制备及表征[J].分析测试学报, 1999,18(4):46-48.
【14】陶冬源,杨修春.氨气热还原法制备氮化钛纳米颗粒[J].化工管理, 2017(5):180-180.
【15】LI W Y, PAN Z C, HUANG Z J, et al. Pt nanoparticles supported on titanium iron nitride nanotubes prepared as a superior electrocatalysts for methanol electrooxidation[J]. International Journal of Hydrogen Energy, 2018,43(20):9777-9786.
【16】XIE Y B, XIA C, DU H X, et al. Enhanced electrochemical performance of polyaniline/carbon/titanium nitride nanowire array for flexible supercapacitor[J]. Journal of Power Sources, 2015,286:561-570.
【17】王炜,陶杰,章伟伟,等.阳极氧化法制备TiO2多孔膜[J].钛工业进展, 2005,22(2):30-33.
【18】DONG S M, CHEN X, GU L, et al. A biocompatible titanium nitride nanorods derived nanostructured electrode for biosensing and bioelectrochemical energy conversion[J]. Biosensors and Bioelectronics, 2011,26(10):4088-4094.
【19】PU J, DU H X, WANG J, et al. High-performance Li-ion Sn anodes with enhanced electrochemical properties using highly conductive TiN nanotubes array as a 3D multifunctional support[J]. Journal of Power Sources, 2017,360:189-195.
【20】WU M M, WEI H Y, WEI Y N, et al. SERS properties of TiN nanotube arrays prepared via reduction nitridation of TiO2 nanotube arrays derived from anodic oxidation method[J]. Vibrational Spectroscopy, 2018,95:32-37.
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