•  
  •  
 

Corresponding Author

Yan-He Han(hanyanhe@bipt.edu.cn)

Abstract

In the traditional Ti/β-PbO2 electrode, the crystal lattice difference between β-PbO2 and Ti matrix is large, and the prepared electrode is easy to fall off and has a short service life. It needs to be modified in actual use. Based on the advantages of α-PbO2 material and Ag material in terms of adhesion and conductivity, respectively, the above two materials are selected as the intermediate layer of Ti/β-PbO2 electrode to improve electrode performance. In this paper, by preparing Ti/α/β-PbO2 and Ti/Ag/β-PbO2 electrodes with different intermediate layers, the superiority and feasibility of electrocatalytic oxidation technology for rapid determination of organic matter (COD) content in simulated glucose wastewater were investigated. Firstly, the properties of the two electrodes were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD) to characterize the surface morphology and crystal structure of the electrodes, respectively. The electrode surfaces of Ti/α/β-PbO2 and Ti/Ag/β-PbO2 had no other granular crystal bare leakage, and their crystal arrangement was relatively compact. Compared with Ti/Ag/β-PbO2, the crystal structure of Ti/α/β-PbO2 electrode surface was more uniform and the grain size was smaller. Secondly, a series of electrochemical performance tests were carried out on the two electrodes by employing linear scanning voltammetry (LSV), Tafel curve analysis, cyclic voltammetry (CV) and AC impedance spectroscopy. The results show that the crystal structure of Ti/α/β-PbO2 electrode surface was more uniform, and the grain size was smaller, and the electroactive surface area was larger. The oxygen evolution potential of Ti/α/β-PbO2 electrode was 1.77 V, which provides a good condition for the formation of ·OH. In Tafel and CV tests, the exchange current density i0 and the specific capacitance CP of Ti/α/β-PbO2 electrode were 0.0995 A·cm-1 and 0.004098 F·cm-1, respectively, which are higher than those of Ti/Ag/β-PbO2 electrode, indicating that Ti/α/β-PbO2 electrode has excellent corrosion resistance and electron releasing ability, Finally, the Ti/α/β-PbO2 electrode was selected as a working electrode. The results show that the optimum conditions for the determination of COD by Ti/α/β-PbO2 electrode were as follows: the oxidation potential 1.30 V, electrolysis time 150 s, electrolyte concentration 0.03 mol·L-1 sodium nitrate (NaNO3). The correlation coefficient of COD measured by electrochemical method and colorimetric digestion method reached 0.9909, and it had good reproductivity and correlation. The detection range of COD was 0 mg·L-1 ~ 500 mg·L-1, which can replace the standard potassium dichromate method within the error allowable range, and provide reference value for the realization of rapid online COD detection. In follow-up studies, actual water samples such as surface water or sewage plant effluent will be compared with the colorimetric digestion method, and attention will be paid to the sensitivity of the electrode after multiple cycles of use.

Graphical Abstract

Keywords

lead dioxide electrode, COD detection, electrocatalytic oxidation, preparation and characterization of electrode

Publication Date

2021-10-28

Online Available Date

2021-05-26

Revised Date

2021-05-22

Received Date

2021-03-26

References

[1] Ma J. Determination of chemical oxygen demand in aqueous samples with non-electrochemical methods[J]. Trends Environ. Anal. Chem., 2017, 14(4): 37-43.
doi: 10.1016/j.teac.2017.05.002 URL

[2] Li C F, Song G W. Photocatalytic degradation of organic pollutants and detection of chemical oxygen demand by fluorescence methods[J]. Sensor. Actuat. B - Chem., 2009, 137(2): 432-436.
doi: 10.1016/j.snb.2009.01.055 URL

[3] Qi M M(齐蒙蒙), Han Y H(韩严和), Sun Q(孙齐). Principle and application of advanced oxidation method for determination of chemical oxygen demand[J]. Environ. Chem.(环境化学), 2019, 38(11): 2481-2497.

[4] Ma C J, Tan F, Zhao H M, Chen S, Quan X. Sensitive amperometric determination of chemical oxygen demand using Ti/Sb-SnO2/PbO2 composite electrode[J]. Sensor. Actuat. B - Chem., 2011, 155(1): 114-119.
doi: 10.1016/j.snb.2010.11.033 URL

[5] Chen J, Liu S, Qi X, Yan S F, Guo Q. Study and design on chemical oxygen demand measurement based on ultraviolet absorption[J]. Sensor. Actuat. B - Chem., 2018, 254(1): 778-784.
doi: 10.1016/j.snb.2017.04.070 URL

[6] Mo H L, Tang Y, Wang X Z, Liu J, Kong D D, Chen Y M, Wan P Y, Cheng H N, Sun T Q, Zhang L Y, Zhang M, Liu S Y, Sun Y Z, Wang N, Xing L X, Wang L, Jiang Y, Xu X, Zhang Y Y, Meng X D. Development of a three-dimensional structured carbon fiber felt/β-PbO2 electrode and its application in chemical oxygen demand determination[J]. Electrochim. Acta, 2015, 176(9): 1100-1107.
doi: 10.1016/j.electacta.2015.07.126 URL

[7] Bogdanowicz R, Czupryniak J, Gnyba M, Ryl J, Ossowski T, Sobaszek M, Darowicki K. Determination of chemical oxygen demand (COD) at boron-doped diamond (BDD) sensor by means of amperometric technique[M]. Procedia Engineering, 2012, 47(9): 1117-1120.

[8] Yang J Q, Chen J W, Zhou Y K, Wu K B. A nano-copper electrochemical sensor for sensitive detection of chemical oxygen demand[J]. Sensor. Actuat. B - Chem., 2011, 153(1): 78-82.
doi: 10.1016/j.snb.2010.10.015 URL

[9] Li X L, Lin D H, Lu K C, Chen X, Yin S Y, Li Y, Zhang Z Y, Tang M H, Chen G S. Graphene oxide orientated by a magnetic field and application in sensitive detection of chemical oxygen demand[J]. Anal. Chim. Acta, 2020, 1122(7): 31-38.
doi: 10.1016/j.aca.2020.05.009 URL

[10] Liang L Q, Yin J, Bao J P, Cong L C, Huang W M, Lin H B, Shi Z. Preparation of Au nanoparticles modified TiO2 nanotube array sensor and its application as chemical oxygen demand sensor[J]. Chinese Chem. Lett., 2019, 30(1): 167-170.
doi: 10.1016/j.cclet.2018.01.049 URL

[11] Zheng Z Y, Yu Q, Chen Z, Zhu W, Hu Q, Liu Y Y, Gui L, Song Y Z. Investigation of localized electrochemical reactivity on a β-PbO2 electrode using scanning electrochemical microscopy[J]. J. Electroanal. Chem., 2020, 878: 114699.
doi: 10.1016/j.jelechem.2020.114699 URL

[12] Zheng Y H, Su W Q, Chen S Y, Wu X Z, Chen X M. Ti/SnO2-Sb2O2-RuO5/α-PbO2/β-PbO2 electrodes for pollutants degradation[J]. Chem. Eng. J., 2011, 174(1): 304-309.
doi: 10.1016/j.cej.2011.09.035 URL

[13] Zhang Y J(张英杰), Liu J M(刘嘉铭), Zhao J B(赵金保), Huang L(黄令), Li X(李雪). Effect of silver loading on lithium storage performance of TiO2 flexible film electrode[J]. Chinese J. Inorg. Chem.(无机化学学报), 2017, 33(5): 809-816.

[14] Wu X L(吴晓玲). Study on the method of analyzing the content of heavy metals in soil by XRF[D]. Chengdu University of Technology(成都理工大学), 2016.

[15] Alderton D. X-ray diffraction(XRD)[M]. United States:Encyclopedia of geology (Second Edition), 2021: 520-531.

[16] Shao C R, Zhang F, Li X, Zhang J H, Jiang Y S, Cheng H Y, Zhu K G. Influence of Cr doping on the oxygen evolution potential of SnO2/Ti and Sb-SnO2/Ti electrodes[J]. J. Electroanal. Chem., 2019, 832(1): 436-443.
doi: 10.1016/j.jelechem.2018.11.058 URL

[17] Bessegato G G, Cooke M D, Christensen P A, Wood D, Zanoni M V B. Synjournal and electrochemical characterization of Si/TiO2/Au composite anode: Efficient oxygen evolution and hydroxyl radicals generation[J]. Electrochim. Acta, 2021, 370: 137742.
doi: 10.1016/j.electacta.2021.137742 URL

[18] Zhang Y C(张一弛), Tang W J(汤文静), Chen Q W(陈倩文), Zhuo M N(卓孟宁), Wang L Z(王立章). Evaluation strategy of electrode performance for electrocatalytic oxidation of organic pollutants[J]. China Environ. Sci.(中国环境科学), 2020, 40(8): 3433-3440.

[19] Mo H L, Tang Y, Wang N, Zhang M, Cheng H N, Chen Y M, Wan P Y, Sun Y Z, Liu S Y, Wang L. Performance improvement in chemical oxygen demand determination using carbon fiber felt/CeO2-β-PbO2 electrode deposited by cyclic voltammetry method[J]. J. Solid State Electro-chem., 2016, 20(8): 2179-2189.

[20] Wang Q(王琴), Wang X C(王晓春), Yang D W(杨冬伟), Li L(李露), Jia Y J(贾友见), Shi J(施锦). Causes of electrode deactivation during CO2 electroreduction on Au electrode[J]. J. Chem. Reaction Eng.&Pro.(化学反应工程与工艺), 2015, 31(4): 352-358.

[21] Liu J H, Han L F, Xu J, Han Z H. Effect of current density on interface structure and performance of CF/β-PbO2 electrodes during zinc electrowinning[J]. Ceram. Int., 2020, 46(2): 2403-2408.
doi: 10.1016/j.ceramint.2019.09.233 URL

[22] Liao D H(廖登辉), Chen Z(陈阵), Guo Z C(郭忠诚), Lu L F(陆丽芳). Preparation of new stainless steel-based lead dioxide - tungsten carbide composite electrode material[J]. Chin. J. Appl. Chem.(应用化学), 2013, 30(2): 196-202.

[23] Zhang W L, Lin H B, Kong H S, Lu H Y, Yang Z, Liu T T. High energy density PbO2/activated carbon asymmetric electrochemical capacitor based on lead dioxide electrode with three-dimensional porous titanium substrate[J]. Int. J. Hydrogen Energ., 2014, 39(30): 17153-17161.
doi: 10.1016/j.ijhydene.2014.08.039 URL

[24] Xu H, Yuan Q S, Shao D, Yang H H. Fabrication and characterization of PbO2 electrode modified with [Fe(CN)6]3- and its application on electrochemical degradation of alkalilignin[J]. J. Hazard. Mater., 2015, 286(25): 509-516.
doi: 10.1016/j.jhazmat.2014.12.065 URL

[25] Vinuth R T N, Hoskeri P A, Muralidhara H B, Prasanna B P, Kumar K Y, Alharthi F A, Raghu M S. Tantalum pentoxide functionalized nitrogen-doped reduced graphene oxide as a competent electrode material for enhanced specific capacitance in a hybrid supercapacitor device[J]. J. Alloy. Compd., 2021, 861(4): 158572.
doi: 10.1016/j.jallcom.2020.158572 URL

[26] Lin J D, Chou C T. The influence of phosphorus content on the microstructure and specific capacitance of etched electroless Ni-P coatings[J]. Surf. Coat. Tech., 2019, 368(6): 126-137.
doi: 10.1016/j.surfcoat.2019.04.009 URL

[27] Yang S, Zhao F Y, Li X R, Cao B K, Mo Y, Chen D M, Chen Y. Electrode structural changes and their effects on capacitance performance during preparation and charge-discharge processes[J]. J. Energy Storage, 2019, 24(8): 100799.
doi: 10.1016/j.est.2019.100799 URL

[28] Iqbal M F, Mahmood U H, Ashiq M N, Iqbal S, Bibi N, Parveen B. High specific capacitance and energy density of synthesized graphene oxide based hierarchical AlS nanorambutan for supercapacitor applications[J]. Electrochim. Acta, 2017, 246(8): 1097-1103.
doi: 10.1016/j.electacta.2017.06.123 URL

[29] Kondo T, Tamura Y, Hoshino M, Watanabe T, Aikawa T, Yuasa M, Einaga Y. Direct determination of chemical oxygen demand by anodic decomposition of organic compounds at a diamond electrode[J]. Anal. Chem., 2014, 86(16): 8066-8072.
doi: 10.1021/ac500919k URL

[30] Yang S Y(杨世迎), Zhang W Y(张文义), Shan L(单良), Yang X(杨鑫), Wang P(王萍). Discussion on Cl- interference in the method of COD detection in landfill leachate[J]. Chin. J. Environ. Sci.(环境科学), 2010, 31(4): 1014-1020.

[31] Ma C J, Tan F, Zhao H M, Chen S, Quan X. Sensitive amperometric determination of chemical oxygen demand using Ti/Sb-SnO2/PbO2 composite electrode[J]. Sensor. Actuat. B - Chem., 2011, 155(1): 114-119.
doi: 10.1016/j.snb.2010.11.033 URL

[32] Xie T(谢天), Dan D Z(旦德忠), Wang B(王斌). Application of Ti/PbO2 electrode in the determination of COD[J]. J. Sichuan Univ.(Eng. Sci. Ed.), 2004, 36(1): 37-40.

[33] Yu H B, Ma C J, Quan X, Chen S, Zhao H M. Flow injection analysis of chemical oxygen demand (COD) by using a boron-doped diamond (BDD) electrode[J]. Environ. Sci. Technol., 2009, 43(6): 1935-1939.
doi: 10.1021/es8033878 URL

Download

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.