【摘要】：近年來,電化學傳感器發(fā)展迅速,與其它分析方法相比,電化學檢測法具有分析速度快、操作簡單、省時且易于實現(xiàn)現(xiàn)場檢測等優(yōu)點。電極修飾材料作為傳感器中最重要的一部分,受到許多研究人員的關(guān)注。本文成功合成NiFe2O4/MWCNTs、ILs@LiFe5O8/MWCNTs、ILs@CdFe2O4/Ni三種復合材料,構(gòu)建新型有機污染物(農(nóng)殘苯菌靈(Benomyl)、雙酚類污染物(雙酚AP(BPAP)、雙酚S(BPS))電化學傳感器,建立了對農(nóng)殘和雙酚類污染物的電化學分析方法,基本工作如下：一步水熱法合成NiFe2O4/MWCNTs復合材料,構(gòu)建NiFe2O4/MWCNTs修飾電極檢測微量／痕量benomyl電化學傳感器。計時庫倫法研究表明,NiFe2O4/MWCNTs修飾電極的有效電催化活性表面積約為裸電極的6倍。采用循環(huán)伏安法(CV)和差分脈沖伏安法(DPV)探究benomyl的電化學行為,NiFe2O4/MWCNTs/GCE 對 benomyl表現(xiàn)出強的電催化效應,揭示電化學反應機制,其電極反應為吸附控制的準可逆電極過程,是兩電子兩質(zhì)子參與的電化學反應。在pH6.0的PBS緩沖溶液中,benomyl峰電流與濃度在100×10-6mol/L～1.00×10-4mol/L范圍內(nèi)呈良好線性關(guān)系,檢出限為2.51×10-7mol/L (S/N=3)。該方法被成功應用于食品樣品中benomyl的檢測,得到滿意結(jié)果,加標回收率在93.2%-101.6%之間,相對標準偏差小于5.3%,該修飾電極在實際應用中具有良好的重現(xiàn)性、穩(wěn)定性。本文建立的電化學傳感器能準確、快速、靈敏地用于benomyl的監(jiān)測。制備ILs@LiFe5O8/MWCNTs修飾電極,建立BPAP的電化學檢測方法,實驗引入離子液體(ILs)構(gòu)建修飾電極,極大提高傳感器的電流響應。用ILs@LiFe5O8/MWCN Ts修飾電極檢測BPAP,結(jié)果表明,修飾電極對BPAP具有較強的電催化活性,BPAP的電極反應為吸附控制的不可逆電極過程,是兩電子兩質(zhì)子參與的電化學反應。在pH 5.0的PBS緩沖溶液中,ILs@LiFe5O8/MWCNTs/GCE對BPAP的線性范圍為1.034×10-9 mol/L～2.069× 10-6 mol/L,檢出限為8.197x10-10 mol/L (S/N=3), ILs@LiFe5O8/MWCNTs/GCE成功用于對實際樣品中BPAP的痕量分析,該方法制備的傳感器具有良好的重現(xiàn)性,穩(wěn)定性和抗干擾能力。成功制備Ni參雜CdFe2O4復合材料,引入具有較寬電化學窗口的離子液體(ILs)包覆CdFe2O4/Ni復合材料,成功構(gòu)筑ILs@CdFe2O4/Ni修飾電極,建立同時檢測B PAP和BPS的分析方法。探究BPAP和BPS在ILs@CdFe2O4/Ni/GCE的電化學行為,BPAP和BPS的氧化峰電位差為310mV,在pH 6.0的PBS緩沖溶液中,實現(xiàn)對BPAP和BPS的同時檢測。ILs@CdFe2O4/Ni/GCE對BPAP的線性范圍為6.89×10-9 mol/L～6.89×10-6 mol/L, BPAP的檢出限為5.37×10-9mol/L (S/N=3); ILs@CdFe2O4/Ni/GCE對BPS的線性范圍為8.00×10-9 mol/L～ 8.00 ×10-6 mol/L,檢出限為7.19×10-9mol/L (S/N=3)。利用該方法對塑料牛奶袋、塑料果汁瓶及塑料包裝袋進行檢測,結(jié)果令人滿意。ILs@CdFe2O4/Ni/GCE具有良好的重現(xiàn)性、穩(wěn)定性和抗干擾能力,該方法具有快速、靈敏、方便的優(yōu)點。
[Abstract]:In recent years, electrochemical sensors have developed rapidly. Compared with other analytical methods, electrochemical detection has the advantages of fast analysis speed, simple operation, time-saving and easy to realize on-the-spot detection. Electrode-modified materials, as the most important part of the sensor, have been concerned by many researchers. In this paper, three kinds of NiFe2O4/MWCNTs,ILs@LiFe5O8/MWCNTs,ILs@CdFe2O4/Ni composites were successfully synthesized, and a new type of organic pollutants (bisphenol AP-(BPAP), bisphenol S-(BPS) was constructed, which is a new kind of organic pollutant (bisphenol AP-(BPAP), bisphenol S-(BPS). A method for electrochemical analysis of agricultural residues and bisphenol pollutants was established. The basic work is as follows: one-step hydrothermal synthesis of NiFe2O4/MWCNTs composites and construction of NiFe2O4/MWCNTs modified electrode for detection of trace / trace benomyl electrochemical sensors. The effective electrocatalytic surface area of the NiFe2O4/MWCNTs modified electrode is about 6 times that of the bare electrode, according to the time-dependent Coulomb method. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to investigate the electrochemical behavior of benomyl. NiFe2O4/MWCNTs/GCE showed strong electrocatalytic effect on benomyl and revealed the mechanism of electrochemical reaction. The electrode reaction is a quasi-reversible electrode process controlled by adsorption, which is an electrochemical reaction involving two electrons and two protons. In the PBS buffer solution of pH6.0, there was a good linear relationship between the peak current of benomyl and the concentration in the range of 100 脳 10-6 mol / L ~ 1.00 脳 10-4mol/L, and the detection limit was 2.51 脳 10-7mol/L (S/N=3). The method has been successfully applied to the determination of benomyl in food samples with satisfactory results. The recovery of standard addition is between 93.2% and 101.6%, and the relative standard deviation is less than 5.3%. The modified electrode has good reproducibility in practical application. Stability. The electrochemical sensor developed in this paper can be used to monitor benomyl accurately, quickly and sensitively. The ILs@LiFe5O8/MWCNTs modified electrode was prepared and the electrochemical detection method of BPAP was established. The ionic liquid (ILs) was introduced to construct the modified electrode, which greatly improved the current response of the sensor. The results of BPAP, detection with ILs@LiFe5O8/MWCN Ts modified electrode show that the modified electrode has strong electrocatalytic activity for BPAP, and the electrode reaction of BPAP is an irreversible electrode process controlled by adsorption, which is an electrochemical reaction involving two electrons and two protons. In PBS buffer solution of pH 5.0, the linear range of ILs@LiFe5O8/MWCNTs/GCE to BPAP was 1.034 脳 10 ~ 9 mol/L~2.069 脳 10 ~ 6 mol/L, the detection limit was 8.197x10-10 mol/L (S/N=3). ILs@LiFe5O8/MWCNTs/GCE has been successfully applied to the trace analysis of BPAP in practical samples. The sensor prepared by this method has good reproducibility, stability and anti-interference ability. Ni-doped CdFe2O4 composites were successfully prepared. Ionic liquid (ILs) coated CdFe2O4/Ni composites with wide electrochemical window were introduced. The ILs@CdFe2O4/Ni modified electrode was successfully constructed and the analytical method for simultaneous detection of B-PAP and BPS was established. The electrochemical behavior of BPAP and BPS in ILs@CdFe2O4/Ni/GCE was investigated. The difference of oxidation peak potential between BPAP and BPS was 310 MV, and in pH 6.0PBS buffer solution, the oxidation peak potential difference between BPAP and BPS was 310 MV. The linear range of ILs @ CdFe2O4/Ni/GCE to BPAP is 6.89 脳 10-9mol/L ~ 6.89 脳 10 脳 10 ~ 6 mol/L, BPAP. The detection limit is 5.37 脳 10-9mol/L (S/N=3) for BPAP and BPS. The linear range of ils @ CdFe2O4/Ni/GCE to BPAP is 6.89 脳 10-9mol/L ~ 6.89 脳 10 ~ 6 mol/L, BPAP. The linear range of ILs@CdFe2O4/Ni/GCE for BPS is 8.00 脳 10-9mol/L ~ 8.00 脳 10 脳 6 mol/L, the detection limit is 7.19 脳 10-9mol/L (S/N=3). The method was used to detect plastic milk bags, plastic juice bottles and plastic bags with satisfactory results. Ils @ CdFe2O4/Ni/GCE has good reproducibility, stability and anti-interference ability. This method is rapid and sensitive. The advantage of convenience.
【學位授予單位】：遼寧大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：X830;O657.1

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