化学需氧量电化学传感器研究  

Research on Electrochemical Chemical Oxygen Demand Sensor

作　　者：貟姗 王磊[1] 万立国[2] 彭振宇 王鸿昌 翟俊峰[1,2,3] 董绍俊 YUN Shan;WANG Lei;WAN Li-Guo;PENG Zhen-Yu;WANG Hong-Chang;ZHAI Jun-Feng;DONG Shao-Jun(State Key Laboratory of Electroanalytical Chemistry,Changchun Instituteof Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;School of WaterConservancy and Environment Engineering,Changchun Institute ofTechnology,Changchun 130022,China;Wastewater Treatment Plant,Changchun FAWComprehensive Utilization Co.Ltd.,Changchun 130011,China;JilinBishuiyuan Environmental Protection Technology Co.Ltd.,Jilin 132011,China)

机构地区：[1]中国科学院长春应用化学研究所,电分析化学国家重点实验室,长春130022 [2]长春工程学院水利与环境工程学院,长春130022 [3]长春一汽综合利用股份有限公司污水处理厂,长春130011 [4]吉林市碧水源环保科技有限公司,吉林132011

出　　处：《分析化学》2024年第9期1298-1306,共9页Chinese Journal of Analytical Chemistry

基　　金：吉林省科技发展计划重点研发项目(No.20230203006SF);吉林省中青年科技创新创业卓越人才团队项目(No.20240601015RC);国家重点研发计划项目(No.2020YFB2009003)资助。

摘　　要：化学需氧量(COD)检测是实现水环境保护与污水处理过程控制的必要措施。本研究将掺杂氟的氧化硒导电玻璃(FTO)/TiO2/PbO2电极与薄层电化学池结合,成功制备了电化学COD传感器用于水体中COD的流动检测。采用电化学分析仪、X-射线光电子能谱仪(XPS)、X-射线衍射仪(XRD)对FTO/TiO2/PbO2电极进行表征。结果表明,在传感器工作初期,输出信号强度的快速衰减与电极表面PbSO4的阳极氧化过程有关。优化了PbO2沉积时间和支持电解质Na2SO4浓度,并进行了实际样品的检测。采用此传感器检测湖水水样和河水水样,传感器信号强度变化规律与国标法《水质化学需氧量的测定快速消解分光光度法》(HJ/T 399—2007)一致,并且当湖水水样被高COD值污水水样替代后,传感器信号显著增大。对COD值为30 mg/L的污水水样连续测量45次,平均值为32.5 mg/L,相对标准偏差为6.8%,测试周期为400 s。所研制的电化学COD传感器具有测试周期可调、测试条件温和以及无需使用有毒有害化学试剂等优点,为水体COD常规检测、有机污染物偷排预警以及污水处理过程控制提供了一种有效的绿色解决方案。An electrochemical chemical oxygen demand(COD)sensor was proposed based on a FTO/TiO2/PbO2 electrode and a thin-layer electrochemical cell.The FTO/TiO2/PbO2 electrode was characterized by X-ray photoelectronic spectroscopy(XPS),X-ray diffraction(XRD)spectroscopy and electrochemical technique,and the results indicated that the rapid decrease in the output signals of the electrochemical COD sensor could be attributed to oxidation of PbSO4 occurring on the surface of FTO/TiO2/PbO2 electrode.The PbO2 deposition time and concentration of Na2SO4 were further optimized and then the electrochemical COD sensor was challenged by real samples including laker water sample,river water sample and wastewater sample.The evolution trend of signals of the electrochemical COD sensor in response to lake and river water samples was identical with that obtained with the standard method(HJ/T399-2007,Water quality-determination of the chemical oxygen demandfast digestion-spectrophotometric method).The electrochemical COD sensor exhibited significant increase in the signal intensity after the samples were switched from lake water to wastewater sample,and a mean value of 32.5 mg/L with relative standard deviation(RSD)of 6.8%were obtained after measuring 45 times the wastewater with COD value of 30 mg/L under a sampling interval of 400 s.The as-prepared electrochemical COD sensor possessed good promise in regular monitoring of COD,discharge of wastewater and industrial process control,with advantages such as a small sampling interval,mild reaction conditions and no requirement of toxic and harmful chemical reagents.

关 键 词：电催化氧化 二氧化铅电极 化学需氧量 化学需氧量传感器 羟基自由基 

分 类 号：X832[环境科学与工程—环境工程] TP212[自动化与计算机技术—检测技术与自动化装置]