TWI479147B - Organic chlorine selection film and manufacturing method thereof - Google Patents
Organic chlorine selection film and manufacturing method thereof Download PDFInfo
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本發明是有關於一種有機氯選擇薄膜及其製備方法，特別是有關於一種利用電漿技術修飾玻璃碳電極以製備出具有選擇性吸附有機氯農藥中之氯苯結構之有機氯選擇薄膜，進而將其應用於電化學農藥快速檢測之領域上。 The invention relates to an organic chlorine selective film and a preparation method thereof, in particular to a method for modifying a glass carbon electrode by using a plasma technology to prepare an organic chlorine selective film having a chlorobenzene structure selectively adsorbing organochlorine pesticides, and further It is applied to the field of rapid detection of electrochemical pesticides.
農藥之使用主要訴求為防止農林作物其產物之病蟲鼠害、雜草者，或用於調節農林作物生長或影響其生理作用者，或用於調節有益昆蟲生長者。自古到今，農業已成為新興國家的經濟基礎，在土地上所耕種之農產品使得人民豐衣足食。 The main use of pesticides is to prevent pests and diseases of agricultural and forestry crops, weeds, or to regulate the growth or influence of agricultural and forestry crops, or to regulate the growth of beneficial insects. Since ancient times, agriculture has become the economic base of emerging countries, and the agricultural products cultivated on the land have made the people rich and well-fed.
隨著人口快速成長，對食物的需求也極速的增加，為了滿足人類對糧食上之需求，就需要更多的耕作空間來獲取更大的收益，而農藥的使用即可解決這個問題。透過適當的農藥使用可防治農產品的病蟲害，但人類過度的使用農要來創造更高產量與經濟價值，導致農藥濫用的情況日益嚴重。農藥毒性能消滅農作物的病蟲害，也會對人體造成 殺傷力，這是一體兩面的，易造成灌溉水與土壤中殘留大量汙染物，且於污染的土地上所耕作之農作物也會有汙染物殘留的問題。 With the rapid population growth, the demand for food is also increasing rapidly. In order to meet the human demand for food, more farming space is needed to obtain greater benefits, and the use of pesticides can solve this problem. The use of appropriate pesticides can control pests and diseases of agricultural products, but the excessive use of agriculture by humans to create higher yields and economic value has led to an increasing number of pesticide abuses. Pesticide toxicity can eliminate pests and diseases of crops, and it will also cause damage to human body. The lethality, which is two-sided, is likely to cause a large amount of pollutants remaining in the irrigation water and soil, and the crops cultivated on the polluted land will also have the problem of residual pollutants.
而農作物殘留之汙染物中，特別是有機污染物(Persistent Organic Pollutants，簡稱POPs)係具有不易分解與生物累積性，對人體與環境產生危害影響。POPs更具有蚱蜢效應(Grasshopper Effect)，是一種高殘留性的污染物，其能經由大氣不斷蒸發及沈降、化學品的使用以及污泥農用等途徑殘留於土壤環境中。即使經過二十多年的自然降解，土壤環境中的POPs殘留量還是相當可觀，尤其是農產品中之含氯有機污染物，更為全球性的問題，國際間皆相當重視。 Among the pollutants residues in crops, especially organic pollutants (Persistent Organic Pollutants, POPs) are not easily decomposed and bioaccumulative, which has harmful effects on the human body and the environment. POPs have a Grasshopper Effect, a highly residual contaminant that can remain in the soil environment through constant evaporation and deposition of the atmosphere, use of chemicals, and sludge farming. Even after more than 20 years of natural degradation, the residual amount of POPs in the soil environment is considerable, especially the chlorinated organic pollutants in agricultural products, which are more global issues, and are highly valued internationally.
因此，目前常用涉及農業資材與產品的檢測方法甚多，諸如層析法、質譜法、電化學分析法、光譜法等，其中以電化學分析法最為快速、簡便，且具備發展為隨測即知感測器的潛力。習知的電化學分析法有著多樣的分析技術，如循環伏安法、安培法等。一般而言，循環伏安法為電位隨時間改變，掃瞄造成電流改變進而完成一張循環伏安圖，並可藉此取得分析物的基本資訊，包括氧化還原電位、電子轉移數等；安培法則係利用施加固定電位的方式進行分析物的測定，若與流動系統或層析法結合，則有利於重複性的偵測工作。 Therefore, there are many detection methods commonly used in agricultural materials and products, such as chromatography, mass spectrometry, electrochemical analysis, spectroscopy, etc. Among them, electrochemical analysis is the fastest, simpler, and has the development to follow the test. Know the potential of the sensor. Conventional electrochemical analysis methods have various analytical techniques, such as cyclic voltammetry and amperometry. In general, cyclic voltammetry is a change in potential over time, which causes a change in current to complete a cyclic voltammogram, and can be used to obtain basic information about the analyte, including redox potential, electron transfer number, etc.; The law uses the application of a fixed potential to determine the analyte. If combined with a flow system or chromatography, it facilitates reproducible detection.
舉例而言，電化學於農藥檢測技術之相關研究概況為以下內容闡述： For example, an overview of the relevant research on electrochemistry in pesticide detection technology is as follows:
(1)Brett等人使用微差脈衝伏安法(differential pulse voltammetry,DPV)及方波伏安法(square wave voltammetry,SWV)來分析除草劑本達隆(bentazon)的殘留量，其係為環境中常見的闊葉類之 選擇性除草劑。在Brett的研究中發現，本達隆除草劑於0.2M之pH 3.4的醋酸(acetate)緩衝溶液中，於+960mV處可得到氧化電流訊號，但隨著實驗操作次數的增加，氧化訊號也越來越小，由此可知本達隆除草劑可能會對電極造成毒化的現象，此處加入Triton界面活性劑後成功的減低毒化現象，提升了分析系統的再現性，在最佳化條件所得到的偵測極限為10μM【Brett et al.,1998,Electrochemical oxidation of bentazon at a glassy carbon electrode Application to the determination of a commercial herbicide.Talanta,46：1131-1135.】。 (1) Brett et al. used differential pulse voltammetry (DPV) and square wave voltammetry (SWV) to analyze the residual amount of the herbicide bentazon, which is Broadleaf Selective herbicide. In Brett's research, it was found that Bendarone herbicide can obtain oxidation current signal at +960mV in 0.2M pH 3.4 acetic acid buffer solution, but as the number of experimental operations increases, the oxidation signal is also increased. The smaller the size, the more the Bendalong herbicide may poison the electrode. The addition of Triton surfactant has successfully reduced the poisoning phenomenon, improved the reproducibility of the analytical system, and obtained the optimized conditions. The detection limit is 10 μM [Brett et al., 1998, Electrochemical oxidation of bentazon at a glassy carbon electrode Application to the determination of a commercial herbicide. Talanta, 46: 1131-1135.].
(2)Schwack將二硫代胺基甲酸鹽和硫代胺基甲酸鹽(thiocarbamate)以熱與酸進行分解，分別讓其生成CS2及COS，再與甲醇六氫砒碇(methanolic piperidine)試劑進行吸附後，以微差脈衝極譜法(diffetential pulse polarograph)的電流測量技術，於E=-0.57和E=-0.36V(vs.Ag/AgCl/(0.1M LiCl))測得CS2及COS的還原訊號【Schwack,1995,Simultaneous differential pulse-polarographic determination of CS2 and COS gases and its application in the analysis of dithiocarbamate fungicide residues in foods.Fresenius' journal of analytical chemistry,351：297-300】。此方法可分析CS2及COS的線性範圍分別為1.5~9.2μM和2.1~12.6μM。 (2) Schwack decomposes the dithiocarbamate and thiocarbamate with heat and acid, respectively, to form CS 2 and COS, and then with methanolic piperidine After the reagent is adsorbed, the CS is measured by the differential pulse polarograph current measurement technique at E=-0.57 and E=-0.36V (vs.Ag/AgCl/(0.1M LiCl)). 2 and COS reduction signal [Schwack, 1995, Simultaneous differential pulse-polarographic determination of CS2 and COS gases and its application in the analysis of dithiocarbamate fungicide residues in foods. Fresenius' journal of analytical chemistry, 351: 297-300]. This method can analyze the linear range of CS 2 and COS as 1.5~9.2 μ M and 2.1~12.6 μ M, respectively.
(3)Besombes等人則是利用電聚合(electropolymerization)的方法【Besombes et al.,1995,A biosensor as warning device for the detection of cyanide,chlorophenols,atrazine and carbamate pesticides.Analytica chimica acta,311：255-263】， 將酪胺酸酵素(tyrosinase)與吡咯兩親性單體(pyrrole amphiphilic monomer)以電化學沉積的方式，在0.1M過氯酸鋰(lithium perchlorate)水溶液中以+0.75V(vs.SCE)的電壓，將酵素沈積在電極表面上。此電極應用來偵測胺基甲酸鹽與亞脫淨農藥時，其偵測極限可達2mM及4mM。 (3) Besombes et al. use electropolymerization [Besombes et al., 1995, A biosensor as warning device for the detection of cyanide, chlorophenols, atrazine and carbamate pesticides. Analytica chimica acta, 311:255- 263], Tyrosinase and pyrrole amphiphilic monomer were electrochemically deposited in a 0.1 M lithium perchlorate aqueous solution at +0.75 V (vs. SCE) The voltage deposits the enzyme on the surface of the electrode. When the electrode is used to detect carbamide and chlorpyrifos pesticides, the detection limit is 2 mM and 4 mM.
(4)Everett和Rechnitz也利用酪胺酸酵素製成的生化感測器來測量有機磷類農藥，其電極的製法是事先在1.0M氫氧化鈉中，以+1.5V的電壓處理後，再將酵素以醯胺(amide)鍵交聯的方式固定在電極表面。完成的電極以1,2-萘醌-4-磺酸鹽(1,2-naphthoquinone-4-sulfonate)當作酵素與電極間之電子傳遞介質(mediator)，此時若加入有機磷類農藥，會因為農藥參與了競爭酵素的反應位置，使得1,2-萘醌-4-磺酸鹽氧化後的產物減少，造成電極上測得的電流減小。以計時安培法(chronoamperometry)在-150mV下分析大利松(diazinon)與二氯松(dichlorvos)的濃度，可分別得到5μM與75nM的偵測極限【Everett & Rechnitz,1998,Mediated bioelectrocatalytic determination of organophosphorus pesticides with a tyrosinase-based oxygen biosensor,Analytical Chemistry,70：807-810.】。 (4) Everett and Rechnitz also use biochemical sensors made of tyrosinase to measure organophosphorus pesticides. The electrode is prepared by treating it with 1.01.5 NaOH in a solution of +1.5V. The enzyme is immobilized on the surface of the electrode by cross-linking with an amide bond. The completed electrode uses 1,2-naphthoquinone-4-sulfonate as the electron transfer medium between the enzyme and the electrode. If an organophosphorus pesticide is added at this time, Because the pesticide participates in the reaction site of the competitive enzyme, the product after oxidation of the 1,2-naphthoquinone-4-sulfonate is reduced, resulting in a decrease in the current measured on the electrode. Analysis of the concentration of dizizon and dichlorvos at -150 mV by chronoamperometry yields detection limits of 5 μM and 75 nM, respectively [Everett & Rechnitz, 1998, Mediated bioelectrocatalytic determination of organophosphorus pesticides With a tyrosinase-based oxygen biosensor, Analytical Chemistry, 70: 807-810.
(5)Priyantha和Weerabahu則發展了一套使用安培法的方式來偵測除草寧，研究中是利用修飾鐵金屬普林類化合物(5,10,15,20-Tetraphenylporphyrinatoiron(III),Fe(III)TPPCl)於玻璃碳電極上，作為除草寧分析物還原的催化劑，並可在施加電位-300mV下偵測除草寧的還原，此分析方法的偵測極限為80μM，而此除草寧化 學感測器的使用生命期可達七個星期【Priyantha & Weerabahu,1996,Amperometric sensor for Propanil.Analytica chimica acta,320：263-268】。 (5) Priyantha and Weerabahu developed a method to detect herbicide by using amperometric method. The study used modified iron metal prion compounds (5,10,15,20-Tetraphenylporphyrinatoiron(III), Fe(III). TPPC1) is used as a catalyst for the reduction of herbicidal analytes on a glassy carbon electrode, and can detect the reduction of herbicidal at an applied potential of -300 mV. The detection limit of this analytical method is 80 μM, and this herbicidal treatment The life of the sensor can be up to seven weeks [Priyantha & Weerabahu, 1996, Amperometric sensor for Propanil. Analytica chimica acta, 320: 263-268].
(6)Teresa等人利用高效能液相層析儀-電子捕獲偵測器(High pressure liquid chromatography-Electron capture detector,HPLC-ECD)之方式偵測對硝基酚(4-nitrophenol)、4,6-二硝基鄰甲基酚(4,6-dinitro-o-cresol,DNOC)、甲基巴拉松(parathion-methyl)、乙基巴拉松(parathion-ethyl)、撲滅松和3-甲基對硝基酚(3-methyl-4-nitrophenol)之六種化合物【Teresa et al.,2000】，其中3-甲基對硝基酚和對硝基酚分別為撲滅松、甲基巴拉松和乙基巴拉松三種農藥的代謝產物，這兩種代謝產物結構相似且具有電活性，因此可以選擇電化學方式進行偵測。第一階段採用庫倫法(coulometry)在工作電極上施加電位為+1.3V(vs.Ag/AgCl)七分鐘，將系統中的干擾物清除以利分析物的還原和偵測。第二階段是使用雙工作電極之流注電化學分析系統，利用流注分析系統可以改善電極被毒化的現象，同樣在上游電極施加-1.3V的電位以清除氧氣的干擾，下游電極則施加電位為+0.7V來定量農藥預分析物，此種電化學分析法最大的缺點就是對分析物沒有選擇性，很容易受到干擾物的影響而失去準確性。Martinez也是利用相同原理偵測撲滅松、甲基巴拉松、乙基巴拉松、Paraoxon(巴拉松之氧化產物)和谷速松(guthion)等五種有機磷類的農藥【Martinez et al.,1993,Automated high-performance liquid chromatographic method for the determination of organophosphorus pesticides in waters with dual electrochemical(reductive-oxidative)detection.Journal of Chromatography A,644：49-58.】。 (6) Teresa et al. used high pressure liquid chromatography-Electron capture detector (HPLC-ECD) to detect 4-nitrophenol, 4, 6-Dinitro-o-cresol (DNOC), parathion-methyl, parathion-ethyl, chlorpyrifos and 3- Six compounds of 3-methyl-4-nitrophenol [Teresa et al., 2000], wherein 3-methyl-p-nitrophenol and p-nitrophenol are respectively putrosten and methyl baba Metabolites of three pesticides, Larsson and Ethyl Barramone, which are structurally similar and electrically active, so electrochemical detection can be selected. The first stage uses coulometry to apply a potential of +1.3V (vs. Ag/AgCl) to the working electrode for seven minutes to remove the interfering substances in the system for analyte reduction and detection. The second stage is a flow injection electrochemical analysis system using a dual working electrode. The flow injection analysis system can improve the poisoning of the electrode. Similarly, a potential of -1.3 V is applied to the upstream electrode to remove oxygen interference, and the downstream electrode is applied with a potential. The pesticide pre-analyte is quantified by +0.7V. The biggest disadvantage of this electrochemical analysis method is that it is not selective for the analyte and is easily affected by the interference and loses accuracy. Martinez also uses the same principle to detect five organophosphorus pesticides such as chlorfenapyr, methylbalazon, ethyl balazon, Paraoxon (oxidation products of balazon) and gution (Martinez et al). 1993,Automated high-performance liquid chromatographic method for the determination of organophosphorus pesticides in waters with dual Electrochemical (reductive-oxidative) detection. Journal of Chromatography A, 644: 49-58.].
(7)Manisankar等人利用多壁碳奈米管(multi-wall carbon nanotubes,MWCNTs)搭配高分子聚合材料聚苯胺(polyaniline,PANI)修飾於玻璃碳電極上，再針對農藥異丙隆(ISOPROTURON)及大克蟎(DICOFOL)，以差式脈衝伏安法進行上述農藥之檢測，其皆有不錯之感測靈敏度，且偵測極限分別為0.1及0.1ppm，但電極容易受到干擾物影響使電流波峰較不明顯【Manisankar,2008,Electroanalysis of some common pesticides using conducting polymer/multiwalled carbon nanotubes modified glassy carbon electrode.Journal of Talanta,76：1022-1028】。 (7) Manisankar et al. used multi-wall carbon nanotubes (MWCNTs) with polyaniline (PANI) modified on glassy carbon electrodes, and then applied to ISOPROTURON. And DICOFOL, the differential pulse voltammetry for the detection of the above pesticides, all have good sensing sensitivity, and the detection limit is 0.1 and 0.1ppm, respectively, but the electrode is susceptible to interference and current The peaks are less pronounced [Manisankar, 2008, Electroanalysis of some common pesticides using conducting polymer/multiwalled carbon nanotubes modified glassy carbon electrode. Journal of Talanta, 76: 1022-1028].
(8)Kim則係利用一導電聚合物(poly(3,4-ethylenedioxythiophene,PEDOT)包覆鈀(Pd)並加以修飾，以於電化學感測電極上進行肼(Hydrazine)之偵測，使用農藥再循環伏安法(Cyclic Voltarnmogram,CV)及安培法(chronoamperometry,CA)等電化學分析方法中，在pH 7.4之磷酸緩衝溶液中，施加-1.5V~+1.5V電壓，在-0.25V之電位處能得到明顯之氧化電流波鋒，且透過PEDOT進行電極修飾可大幅降背景干擾值之產生，同時可得到4×10-8M偵測極限【Kim et al.,2011,Electrocatalytic determination of hydrazine by a glassy carbon electrode modified with PEDOP/MWCNTs-Pd nanoparticles.Sensors and Actuators B：Chemical,153：246-251】。 (8) Kim uses a conductive polymer (poly(3,4-ethylenedioxythiophene, PEDOT) coated palladium (Pd) and modified to detect hydrazine on the electrochemical sensing electrode. In the electrochemical analysis methods such as Cyclic Voltarnmogram (CV) and chronoamperometry (CA), a voltage of -1.5V~+1.5V is applied in a pH 7.4 phosphate buffer solution at -0.25V. The potential of the oxidation current can be obtained at the potential, and the electrode modification by PEDOT can greatly reduce the background interference value and obtain the detection limit of 4×10-8M [Kim et al., 2011, Electrocatalytic determination of hydrazine By a glassy carbon electrode modified with PEDOP/MWCNTs-Pd nanoparticles. Sensors and Actuators B: Chemical, 153: 246-251.
然而，近幾年發現大部份農藥的分析方法都集中在氣相層析儀(gas chromatography,GC)和高效能液相層析儀(High pressure liquid chromatography,HPLC)的應用上，且皆透過施加固定電位以偵測氧化還原電位或電子轉移數等方式進行農藥檢測，但這些分析方法中之主要缺點除了所需操作時間較長之外，且其對於分析物無較佳之選擇性，易受到干擾物之影響，使偵測失去準確性，效益亦不佳。因此，有鑑於習知技術之問題，本發明人便提出一種利用電漿技術製備出具有選擇性吸附有機氯農藥中之氯苯結構之有機氯選擇薄膜，並將其應用於農藥快速檢測之領域。 However, in recent years, most pesticides have been found to be concentrated in gas chromatography (GC) and high pressure liquid chromatography (HPLC) applications. Pesticide detection is carried out by applying a fixed potential to detect the redox potential or the number of electron transfer, but the main disadvantages of these analytical methods are that they have a better selectivity for the analyte and are less susceptible to the analyte. The effects of interferences make the detection lose accuracy and the benefits are not good. Therefore, in view of the problems of the prior art, the inventors have proposed an organochlorine selective film having a chlorobenzene structure selectively adsorbed in organochlorine pesticides by using plasma technology, and applied to the field of rapid detection of pesticides. .
有鑑於上述習知技藝之問題，本發明之目的就是在提供一種有機氯選擇薄膜及其製備方法，其係利用電漿技術將玻璃碳電極進行修飾，以製備出具有符合有機氯農藥之氯苯結構大小之孔洞的有機氯選擇薄膜，藉此使有機氯選擇薄膜可選擇性吸附有機氯農藥中之氯苯結構，以提升偵測有機氯農藥之靈敏度及選擇性，並可應用於電化學農藥快速檢測，以解決習知電化學農藥檢測法之操作時間較長，且對分析物無較佳之選擇性，易受到干擾物之影響，使偵測失去準確性，進而造成檢測效益不佳之問題。 In view of the above problems of the prior art, the object of the present invention is to provide an organochlorine selective film and a preparation method thereof, which are characterized in that a glassy carbon electrode is modified by a plasma technique to prepare a chlorobenzene having an organochlorine pesticide. The organic chlorine selective film of the pore size of the structure, thereby allowing the organic chlorine selective film to selectively adsorb the chlorobenzene structure in the organochlorine pesticide, thereby improving the sensitivity and selectivity of detecting the organochlorine pesticide, and being applicable to the electrochemical pesticide Rapid detection to solve the problem of the long-term operation of the conventional electrochemical pesticide detection method, and has no better selectivity for the analyte, is susceptible to interference, and causes the detection to lose accuracy, thereby causing poor detection efficiency.
根據本發明之目的，提出一種有機氯選擇薄膜之製備方法，其係包含下列步驟：將玻璃碳電極置於電極活化溶液中並施加電位，進行電極活化處理；將含有多壁奈米碳管材料之懸浮液滴於經電極活化處理後之玻璃碳電極上，待乾燥後以得到多壁奈米碳管-玻璃碳修飾電 極；將CF4或NH2基團沉積於三甲矽烷基薄膜上，以形成氧化物層，使其具有專一性選擇有機氯農藥之特性；改質氧化物層之表面，以得到具有改質表面之電漿薄膜；以及將電漿薄膜沉積於多壁奈米碳管-玻璃碳修飾電極上，進而製得具有選擇性吸附有機氯農藥中之氯苯結構之有機氯選擇薄膜。 According to the object of the present invention, a method for preparing an organic chlorine selective film is provided, which comprises the steps of: placing a glassy carbon electrode in an electrode activation solution and applying a potential to perform electrode activation treatment; and containing a multi-walled carbon nanotube material The suspended liquid droplets are deposited on the glassy carbon electrode after the electrode activation treatment, to be dried to obtain a multi-walled carbon nanotube-glassy carbon modified electrode; and the CF 4 or NH 2 group is deposited on the trimethyl decyl group film to Forming an oxide layer to specifically select the characteristics of the organochlorine pesticide; modifying the surface of the oxide layer to obtain a plasma film having a modified surface; and depositing a plasma film on the multi-walled carbon nanotube - On the glassy carbon modified electrode, an organochlorine selective film having a chlorobenzene structure selectively adsorbing organochlorine pesticides was prepared.
較佳地，形成氧化物層之步驟係利用電漿技術將CF4或NH2基團沉積於三甲矽烷基薄膜上，使其具有專一性選擇有機氯農藥之特性。 Preferably, the step of forming the oxide layer is to deposit a CF 4 or NH 2 group on the trimethyl decyl film by a plasma technique to impart specificity to the characteristics of the organochlorine pesticide.
較佳地，利用電漿技術將電漿薄膜沉積於多壁奈米碳管-玻璃碳修飾電極上。 Preferably, the plasma film is deposited on the multi-walled carbon nanotube-glass carbon modified electrode by plasma technology.
較佳地，利用氨氣及四氟化碳之氣體將沉積於全氟化高分子薄膜上之氧化物層之表面進行改質，以得到具有改質表面之電漿薄膜。 Preferably, the surface of the oxide layer deposited on the perfluorinated polymer film is modified with a gas of ammonia gas and carbon tetrafluoride to obtain a plasma film having a modified surface.
較佳地，電漿薄膜之表面係具有複數個孔洞，且經表面改質後之電漿薄膜上之複數個孔洞係符合有機氯農藥中之氯苯結構大小。 Preferably, the surface of the plasma film has a plurality of holes, and the plurality of holes on the surface-modified plasma film conform to the structure of the chlorobenzene in the organochlorine pesticide.
較佳地，電極活化溶液可為氫氧化鈉溶液。 Preferably, the electrode activation solution can be a sodium hydroxide solution.
較佳地，懸浮液包含多壁奈米碳管材料及介面活性劑。 Preferably, the suspension comprises a multi-walled carbon nanotube material and an interfacial surfactant.
較佳地，介面活性劑可為十二烷基硫酸鈉溶液。 Preferably, the surfactant can be a sodium lauryl sulfate solution.
根據本發明之目的，再提出一種有機氯選擇薄膜，其係應用於電化學農藥快速檢測，係包含：玻璃碳電極層、多壁奈米碳管層以及電漿薄膜層。多壁奈米碳管層係設於玻璃碳電極層上。電漿薄膜層係設於多壁奈米碳管層上，且電漿薄膜層之表面係具有符合有機氯農藥中之氯苯結構大小之複數個孔洞。其中，利用電漿技術將多壁奈米碳管層沉積於玻璃碳電極層上，將電漿薄膜層沉積於多壁奈米碳管層上，且電漿薄膜層之表面可透過氨氣及四氟化碳之氣體進行表面改質。 According to the object of the present invention, an organic chlorine selective film is further applied to the rapid detection of electrochemical pesticides, which comprises: a glassy carbon electrode layer, a multi-walled carbon nanotube layer and a plasma film layer. The multi-walled carbon nanotube layer is provided on the glassy carbon electrode layer. The plasma film layer is disposed on the multi-walled carbon nanotube layer, and the surface of the plasma film layer has a plurality of holes conforming to the size of the chlorobenzene structure in the organochlorine pesticide. Wherein, the multi-walled carbon nanotube layer is deposited on the glassy carbon electrode layer by using plasma technology, and the plasma film layer is deposited on the multi-walled carbon nanotube layer, and the surface of the plasma film layer is permeable to ammonia gas and The carbon tetrafluoride gas is surface modified.
較佳地，電漿薄膜層可由高分子材料與氧化物所構成。 Preferably, the plasma film layer may be composed of a polymer material and an oxide.
較佳地，高分子材料可為全氟化聚合物。 Preferably, the polymeric material can be a perfluorinated polymer.
較佳地，氧化物可為三甲矽烷基氧化物。 Preferably, the oxide can be a trimethyl decyl oxide.
承上所述，依本發明之有機氯選擇薄膜及其製備方法，其係利用電漿技術修飾玻璃碳電極，進而製備出具有符合有機氯農藥中氯苯結構大小之孔洞的有機氯選擇薄膜。再將本發明所述之有機氯選擇薄膜應用於電化學農藥快速檢測之領域上，藉此提升有機氯農藥檢測之選擇性、靈敏度、再現性、偵測極限及準確性，以提供使用者簡易地進行農藥快速檢測分析。 According to the invention, the organochlorine selective film according to the invention and the preparation method thereof are characterized in that the glassy carbon electrode is modified by a plasma technique, and an organochlorine selective film having pores conforming to the structure of the chlorobenzene in the organochlorine pesticide is prepared. The organic chlorine selective film of the invention is applied to the field of rapid detection of electrochemical pesticides, thereby improving the selectivity, sensitivity, reproducibility, detection limit and accuracy of organochlorine pesticide detection, so as to provide users with simple Rapid detection and analysis of pesticides.
S11~S15‧‧‧步驟 S11~S15‧‧‧Steps
100‧‧‧有機氯選擇薄膜 100‧‧‧Organic chlorine selective film
110‧‧‧玻璃碳電極 110‧‧‧Glass carbon electrode
120‧‧‧多壁奈米碳管 120‧‧‧Multi-walled carbon nanotubes
130‧‧‧電漿薄膜層 130‧‧‧ Plasma film layer
131‧‧‧孔洞 131‧‧‧ holes
2‧‧‧輔助電極 2‧‧‧Auxiliary electrode
4‧‧‧工作電極 4‧‧‧Working electrode
5‧‧‧參考電極 5‧‧‧ reference electrode
第1圖 係為本發明有機氯選擇薄膜之製備方法之流程圖。 Figure 1 is a flow chart showing the preparation method of the organic chlorine selective film of the present invention.
第2圖 係為本發明有機氯選擇薄膜之結構圖。 Fig. 2 is a structural view of the organic chlorine selective film of the present invention.
第3圖 係為本發明利用循環伏安法找尋有機氯農藥中之氯苯之氧化電位之分析圖。 Fig. 3 is an analysis diagram of the oxidation potential of chlorobenzene in organochlorine pesticides by cyclic voltammetry.
第4A圖 係為本發明利用線性掃描伏安法檢測經強酸電極活化處理後之玻璃碳電極對有機氯農藥中之氯苯結構偵測之選擇性分析圖。 Fig. 4A is a selective analysis diagram of the detection of chlorobenzene structure in organochlorine pesticides by a glassy carbon electrode after activation by a strong acid electrode by linear sweep voltammetry.
第4B圖 係為本發明利用線性掃描伏安法檢測經強鹼電極活化處理後之玻璃碳電極對有機氯農藥中之氯苯結構偵測之選擇性分析圖。 Figure 4B is a selective analysis diagram of the detection of chlorobenzene structure in organochlorine pesticides by a glassy carbon electrode after activation by a strong alkali electrode by linear sweep voltammetry.
第5圖之(A)-(D) 係為本發明利用掃描式電子顯微鏡照射經電極活化處理後以電漿技術將多壁奈米碳管修飾於玻璃碳電極上之晶相圖。 Fig. 5(A)-(D) is a crystal phase diagram of the invention in which a multi-walled carbon nanotube is modified on a glassy carbon electrode by a plasma technique after being subjected to electrode activation treatment by a scanning electron microscope.
第6圖 係為本發明利用多壁奈米碳管進行不同修飾次數之多壁奈米碳管-玻璃碳修飾電極連續偵測有機氯農藥中之氯苯結構之再現性分析圖。 Fig. 6 is a reproducibility analysis diagram of the continuous detection of chlorobenzene structure in organochlorine pesticides by multi-walled carbon nanotube-glassy carbon modified electrode using multi-walled carbon nanotubes.
第7圖 係為本發明經電極活化處理及5次多壁奈米碳管修飾後之有機氯選擇薄膜相較未修飾玻璃碳電極以偵測有機氯農藥中之氯苯結構之電流之靈敏度分析圖。 Figure 7 is a sensitivity analysis of the current of the organochlorine selective film modified by the electrode activation treatment and the modified multi-walled carbon nanotubes to detect the chlorobenzene structure in the organochlorine pesticide. Figure.
第8圖 係為本發明經電極活化處理及5次多壁奈米碳管修飾後之有機氯選擇薄膜偵測不同濃度下之有機氯農藥中之氯苯結構之偵測極限分析圖。 Fig. 8 is a graph showing the detection limit analysis of the chlorobenzene structure in the organochlorine pesticides at different concentrations by the electrode activation treatment and the 5 times multi-walled carbon nanotube modified organochlorine selective film.
第9圖 係為本發明所述之有機氯選擇薄膜應用於電化學農藥檢測器中作為工作電極之示意圖。 Figure 9 is a schematic view showing the organochlorine selective film of the present invention applied to an electrochemical pesticide detector as a working electrode.
為利 貴審查員瞭解本發明之技術特徵、內容與優點及其所能達成之功效，茲將本發明配合附圖，並以實施例之表達形式詳細說明如下。 The technical features, contents, and advantages of the present invention, as well as the advantages thereof, will be apparent to those skilled in the art, and the present invention will be described in detail with reference to the accompanying drawings.
請參閱第1圖，其係為本發明有機氯選擇薄膜之製備方法之流程圖。此實施例中，該製備方法包含下列步驟：步驟S11：將玻璃碳電極置於電極活化溶液中並施加電位，進行電極活化處理。步驟S12：將含有多壁奈米碳管材料之懸浮液滴於經電極活化處理後之玻璃碳電極上，待乾燥後以得到多壁奈米碳管-玻璃碳修飾電極。步驟S13：將CF4或NH2基團沉積於三甲矽烷基薄膜上，以形成氧化物層，使其具有專一性選擇有機氯農藥之特性。步驟S14：改質氧化物層之表面，以得到具有有機氯 農藥專一選擇性之電漿薄膜。步驟S15：將此具有有機氯農藥專一選擇性電漿薄膜沉積於多壁奈米碳管-玻璃碳修飾電極上，進而製得具有選擇性吸附有機氯農藥中之氯苯結構之有機氯選擇薄膜修飾電極。如此一來，藉由上述方法所製成之有機氯選擇薄膜，其係具有偵測之選擇性高、再現性佳、靈敏度高及偵測極限大之優點。 Please refer to FIG. 1 , which is a flow chart of a method for preparing an organochlorine selective film of the present invention. In this embodiment, the preparation method comprises the following steps: Step S11: placing a glassy carbon electrode in an electrode activation solution and applying a potential to perform an electrode activation treatment. Step S12: dropping a suspension containing the multi-walled carbon nanotube material onto the glassy carbon electrode after the electrode activation treatment, and drying to obtain a multi-walled carbon nanotube-glassy carbon modified electrode. Step S13: depositing a CF 4 or NH 2 group on the trimethyl decyl film to form an oxide layer, which has the property of specifically selecting an organochlorine pesticide. Step S14: modifying the surface of the oxide layer to obtain a plasma film having specific selectivity for organochlorine pesticides. Step S15: depositing an organochlorine pesticide-specific selective plasma film on a multi-walled carbon nanotube-glassy carbon modified electrode to prepare an organochlorine selective film having a chlorobenzene structure selectively adsorbing organochlorine pesticides Modify the electrode. In this way, the organochlorine selective film prepared by the above method has the advantages of high detection selectivity, good reproducibility, high sensitivity and large detection limit.
一般而言，玻璃碳電極(glassy carbon electrode,GCE)容易出現電極鈍化及再現性低等現象。所以，目前習知電化學快速檢測法係利用多壁奈米碳管(multi-walled carbon nanotubes,MWCNTs)修飾於玻璃碳電極上，使之具有高導電性、高比表面積及化學穩定性，有利於玻璃碳電極在電化學分析時之電子傳遞，以提高偵測靈敏度。然，目前雖有透過多壁奈米碳管進行玻璃碳電極修飾以提高偵測靈敏度，但一般多壁奈米碳管與玻璃碳電極之修飾係透過分子間之凡得瓦爾力(Van der Waals force)來進行鍵結，其鍵結力較差易掉落，故一般多壁奈米碳管不易修飾在玻璃碳電極上。 In general, a glassy carbon electrode (GCE) is prone to electrode passivation and low reproducibility. Therefore, the conventional electrochemical rapid detection method utilizes multi-walled carbon nanotubes (MWCNTs) modified on a glassy carbon electrode to have high conductivity, high specific surface area and chemical stability. Electron transfer in the electrochemical analysis of glassy carbon electrodes to improve detection sensitivity. However, although glass carbon electrode modification is carried out through multi-walled carbon nanotubes to improve detection sensitivity, the modification of multi-walled carbon nanotubes and glassy carbon electrodes is generally transmitted through the intermolecular Van der Waals. Force) to carry out the bonding, the bonding force is relatively easy to fall, so generally the multi-walled carbon nanotubes are not easily modified on the glassy carbon electrode.
因此，本發明為避免修飾電極於農藥檢測時常出現修飾材料脫落之現象，係於步驟S11中，預先將玻璃碳電極進行電極活化處理之步驟，以使多壁奈米碳管能穩固的吸附於玻璃碳電極上，亦可提升偵測農藥時的電流穩定度。其中，本發明所述之電極活化處理之步驟，係透過酸鹼活化作用，使多壁奈米碳管與玻璃碳電極產生共價鍵，並透過此共價鍵來產生較強之鍵結力，進而增加玻璃碳電極之修飾次數，以提高偵測靈敏度。而本發明在此係利用濃度0.3M~0.5M之氫氧化鈉(NaOH)溶液作為電極活化溶液，其僅係為較佳之實施態樣，但本發明不以此述為限，亦可以濃度0.3M~0.5M之硫酸溶液作為電極活化溶液。且當玻璃碳電極置入於NaOH電極活化溶液時，係利用恆電位安培法 (Amperometric i-t Curve)依0.1V/S之速度，施加+1.2V之電位至所述玻璃碳電極上，以進行電極活化，經10~30分鐘後，以完成該玻璃碳電極之電極活化處理。 Therefore, in order to avoid the phenomenon that the modified electrode is often detached from the modified electrode during the detection of the pesticide, the step of performing the electrode activation treatment on the glassy carbon electrode in advance in step S11 is performed to enable the multi-walled carbon nanotube to be stably adsorbed. The glass carbon electrode also enhances the current stability when detecting pesticides. Wherein, the electrode activation treatment step of the present invention transmits a covalent bond between the multi-walled carbon nanotube and the glassy carbon electrode through acid-base activation, and generates a strong bonding force through the covalent bond. In turn, the number of times of modification of the glassy carbon electrode is increased to improve the detection sensitivity. However, the present invention utilizes a sodium hydroxide (NaOH) solution having a concentration of 0.3 M to 0.5 M as an electrode activation solution, which is only a preferred embodiment, but the invention is not limited thereto, and may have a concentration of 0.3. A sulfuric acid solution of M~0.5M is used as an electrode activation solution. And when the glassy carbon electrode is placed in the NaOH electrode activation solution, the constant potential amperometric method is used. (Amperometric i-t Curve) A potential of +1.2 V was applied to the glassy carbon electrode at a rate of 0.1 V/s to perform electrode activation, and after 10 to 30 minutes, the electrode activation treatment of the glassy carbon electrode was completed.
更進一步地，本發明於步驟S11前，更可將玻璃碳電極先進行電極之表面拋光、清洗等步驟，以使玻璃碳電極之表面更易進行後續修飾動作。其中，本發明所述電極表面拋光之步驟，係將所述之玻璃碳電極利用微絨纖維布進行拋光20分鐘，以去除玻璃碳電極表面之雜質。接著，再將拋光後之玻璃碳電極置入於95%乙醇中，以超音波震盪15分鐘後，即可去除沉澱於電極表面之有機物質，藉此可降低電極受干擾之情形。如此一來，可使得後續的多壁奈米碳管修飾作業更容易執行。以上僅係為較佳之實施態樣，但不應以此述而有所限制者。 Furthermore, in the present invention, before the step S11, the glassy carbon electrode may be subjected to the steps of polishing, cleaning, etc. of the electrode to make the surface of the glassy carbon electrode easier to perform subsequent modification. Wherein, in the step of polishing the surface of the electrode of the present invention, the glassy carbon electrode is polished by a micro-wool fiber cloth for 20 minutes to remove impurities on the surface of the glassy carbon electrode. Then, the polished glassy carbon electrode is placed in 95% ethanol, and after being ultrasonically oscillated for 15 minutes, the organic substance deposited on the surface of the electrode can be removed, thereby reducing the interference of the electrode. As a result, subsequent multi-walled carbon nanotube modification operations can be performed more easily. The above is only a preferred embodiment, but should not be construed as limiting.
當完成玻璃碳電極之電極活化處理後，係執行後續多壁奈米碳管修飾玻璃碳電極之步驟。於步驟S12中，係取5mg的多壁奈米碳管材料溶於50mL之懸浮液中，並以超音波震盪24小時，進而得到依重量比1：10均勻分散之多壁奈米碳管/懸浮液(MWCNTs/suspensions)。其中所述懸浮液可為0.1M十二烷基硫酸鈉溶液之介面活性劑，但不以此為限制。接著，再取5μL之多壁奈米碳管/懸浮液滴於經電極活化處理後之玻璃碳電極上，以與玻璃碳電極產生共價鍵結力，使多壁奈米碳管可穩固地修飾於玻璃碳電極上，並置於50℃烘箱中待溶液蒸發，以蒸餾水沖洗及去除玻璃碳電極之表面上的介面活性劑，待乾燥後即完成多壁奈米碳管-玻璃碳(MWCNTs/GCE)修飾電極之製備。而反覆地重複上述步驟可製備成不同修飾次數之多壁奈米碳管-玻璃碳(MWCNTs/GCE)修飾電極。 After the electrode activation treatment of the glassy carbon electrode is completed, the step of modifying the glassy carbon electrode with the subsequent multi-walled carbon nanotube is performed. In step S12, 5 mg of the multi-walled carbon nanotube material is dissolved in a 50 mL suspension, and ultrasonically oscillated for 24 hours, thereby obtaining a multi-walled carbon nanotubes uniformly dispersed according to a weight ratio of 1:10/ Suspensions (MWCNTs/suspensions). Wherein the suspension may be a surfactant of 0.1 M sodium lauryl sulfate solution, but is not limited thereto. Subsequently, then take as much as 5 μ L SWNT / aerosol droplets to the glass carbon electrode by the activation of the electrode, to produce covalent bonding force with a glassy carbon electrode, so that carbon nanotubes may be multiwall It is firmly modified on the glassy carbon electrode and placed in an oven at 50 ° C to evaporate the solution. The surfactant on the surface of the glassy carbon electrode is rinsed with distilled water and the multi-walled carbon nanotube-glass carbon is completed after drying. Preparation of MWCNTs/GCE) modified electrode. Repeating the above steps repeatedly can produce multi-walled carbon nanotube-glassy carbon (MWCNTs/GCE) modified electrodes with different modification times.
進一步地，本發明係利用線性掃描伏安法(Linear Sweep Voltammetry,LSV)來檢視經強酸(H2SO4)或強鹼(NaOH)電極活化後以多壁奈米碳管修飾之玻璃碳電極，其對偵測有機氯農藥中之氯苯結構的電流波峰情形，如第4A圖及第4B圖所示。由實驗結果顯示，經強鹼電極活化處理後之玻璃碳電極，其吸附多壁奈米碳管之效果較經強酸電極活化處理後之玻璃碳電極明顯，再檢測氯苯時也能得到較明顯的波峰電流，顯示本發明多壁奈米碳管修飾於玻璃碳電極上之效果較佳。且藉此可大幅降低背景值干擾，避免干擾波峰之產生，以增加玻璃碳電極偵測之導電表面積，提升待測標的物之專一性結合，進而提高偵測有機氯農藥之選擇性。 Further, the present invention utilizes Linear Sweep Voltammetry (LSV) to examine a glassy carbon electrode modified with a multi-walled carbon nanotube after activation by a strong acid (H2SO4) or a strong alkali (NaOH) electrode, The current peaks of the chlorobenzene structure in organochlorine pesticides are detected as shown in Figures 4A and 4B. The experimental results show that the effect of adsorbing multi-walled carbon nanotubes on the glassy carbon electrode after activation by the strong alkali electrode is more obvious than that of the glassy carbon electrode after activation by the strong acid electrode, and it can be more obvious when detecting chlorobenzene. The peak current shows that the multi-walled carbon nanotube of the present invention is preferably modified on a glassy carbon electrode. Moreover, the background value interference can be greatly reduced, the interference peak can be avoided, the conductive surface area detected by the glass carbon electrode can be increased, and the specific combination of the objects to be tested can be improved, thereby improving the selectivity of detecting the organochlorine pesticide.
而本發明所述之多壁奈米碳管-玻璃碳(MWCNTs/GCE)修飾電極於掃描式電子顯微鏡(Scanning Electron Microscope,SEM)下之晶相圖，如第5圖之(A)-(D)所示。其中，第5圖之(A)表示：多壁奈米碳管修飾於玻璃碳電極上之10,000倍之晶相圖；(B)表示：多壁奈米碳管修飾於玻璃碳電極上之50,000倍之晶相圖；(C)表示：多壁奈米碳管修飾於玻璃碳電極上並吸附氯苯(CB)之10,000倍之晶相圖；(D)表示：多壁奈米碳管修飾於玻璃碳電極上並吸附氯苯(CB)之50,000倍之晶相圖。藉由第5圖之晶相圖所示，可證明經本發明所述之修飾步驟所製備而成之多壁奈米碳管-玻璃碳(MWCNTs/GCE)修飾電極中，其中所述之多壁奈米碳管確實可有效地沉積於玻璃碳電極上。 The multi-walled carbon nanotube-glassy carbon (MWCNTs/GCE) modified electrode according to the present invention is a crystal phase diagram under a scanning electron microscope (SEM), as shown in FIG. 5(A)-( D) is shown. (A) in Fig. 5 shows a 10,000-fold crystal phase diagram of a multi-walled carbon nanotube modified on a glassy carbon electrode; (B) shows that a multi-walled carbon nanotube is modified on a glassy carbon electrode by 50,000. (C) shows: multi-walled carbon nanotubes modified on a glassy carbon electrode and adsorbed 10,000 times the crystal phase of chlorobenzene (CB); (D) means: multi-walled carbon nanotube modification A phase diagram of 50,000 times that of chlorobenzene (CB) was adsorbed on a glassy carbon electrode. The multi-walled carbon nanotube-glassy carbon (MWCNTs/GCE) modified electrode prepared by the modification step of the present invention can be proved by the crystal phase diagram of FIG. 5, wherein the multi-wall is described The carbon nanotubes are indeed effectively deposited on the glassy carbon electrode.
此外，本發明反覆地重複上述修飾玻璃碳電極之步驟，可製備成不同修飾次數之多壁奈米碳管-玻璃碳(MWCNTs/GCE)修飾電極。請參閱第6圖，其係為本發明利用多壁奈米碳管進行不同修飾次數之多壁奈米碳管-玻璃碳修飾電極連續偵測有機氯農藥中之氯苯結構之再 現性分析圖。在此，本發明利用多壁奈米碳管以修飾玻璃碳電極之次數可分為1次修飾、3次修飾、5次修飾及7次修飾，但不應以此述有所限制。而經過不同修飾次數所得之玻璃碳電極，其連續偵測有機氯農藥中之氯苯結構後的再現性亦不同，如第6圖所示。由實驗結果可得知，相較於修飾1、3、及7次之結果，以多壁奈米碳管重覆修飾玻璃碳電極5次時，經過100次連續偵測有機氯農藥之氯苯結構後，可保留偵測之最佳再現性。故，本發明所述之有機氯選擇薄膜之製備方法中，於步驟S13至步驟S15前，係將玻璃碳電極利用多壁奈米碳管修飾5次作為較佳之實施態樣，但不應此述而有所限制。 In addition, the present invention repeatedly repeats the above steps of modifying the glassy carbon electrode, and can prepare a multi-walled carbon nanotube-glassy carbon (MWCNTs/GCE) modified electrode with different modification times. Please refer to FIG. 6 , which is a multi-walled carbon nanotube-glass carbon modified electrode with multi-walled carbon nanotubes for continuous detection of chlorobenzene structure in organochlorine pesticides. Analysis of the present situation. Here, the number of times the present invention utilizes a multi-walled carbon nanotube to modify a glassy carbon electrode can be divided into one modification, three modifications, five modifications, and seven modifications, but should not be limited thereto. The glassy carbon electrode obtained after different modification times has different reproducibility after continuously detecting the structure of chlorobenzene in the organochlorine pesticide, as shown in Fig. 6. It can be seen from the experimental results that the chlorobenzene of the organochlorine pesticide was continuously detected 100 times when the glassy carbon electrode was repeatedly modified by multi-walled carbon nanotubes 5 times compared with the results of the modification of 1, 3, and 7 times. After the structure, the best reproducibility of the detection can be retained. Therefore, in the preparation method of the organic chlorine selective film according to the present invention, before the step S13 to the step S15, the glassy carbon electrode is modified by using a multi-walled carbon nanotube 5 times as a preferred embodiment, but this should not be the case. There are limits to the description.
因此，於步驟S13至步驟S15中，先將CF4或NH2基團沉積於三甲矽烷基薄膜上，以形成氧化物層，使其具有專一性選擇有機氯農藥之特性，並利用電漿技術將所述氧化物層進行表面改質，以製得具有表面改質之電漿薄膜。接著，再利用電漿技術將所述電漿薄膜沉積於經5次多壁奈米碳管修飾後之多壁奈米碳管-玻璃碳(MWCNTs/GCE)修飾電極上。其中，電漿薄膜之表面改質之步驟，係利用氨氣(NH3)及四氟化碳(CF4)之氣體將沉積於全氟化高分子薄膜上之該氧化物層之表面進行改質。而電漿薄膜之表面可具有複數個孔洞，且經表面改質後之電漿薄膜上之複數個孔洞係符合有機氯農藥中之氯苯結構大小，故本發明所述之方法所製得之有機氯選擇薄膜可具有選擇性吸附有機氯農藥中之氯苯結構之特性。 Therefore, in steps S13 to S15, a CF 4 or NH 2 group is first deposited on the trimethyl decyl film to form an oxide layer, which has the specific property of selecting an organochlorine pesticide, and utilizes plasma technology. The oxide layer is surface modified to produce a plasma film having a surface modification. Next, the plasma film was deposited by a plasma technique on a multi-walled carbon nanotube-glassy carbon (MWCNTs/GCE) modified electrode modified by 5 times of multi-walled carbon nanotubes. Wherein, the step of modifying the surface of the plasma film is to change the surface of the oxide layer deposited on the perfluorinated polymer film by using a gas of ammonia (NH 3 ) and carbon tetrafluoride (CF 4 ). quality. The surface of the plasma film may have a plurality of holes, and the plurality of holes on the surface-modified plasma film conform to the structure of the chlorobenzene in the organochlorine pesticide, so the method of the invention is The organochlorine selective film can have the property of selectively adsorbing the chlorobenzene structure in the organochlorine pesticide.
依據本發明所述之方法所製得之有機氯選擇薄膜之結構，如第2圖所示。而其中所使用之圖式，其主旨僅為示意及輔助說明書之用，未必為本發明實施後之真實比例與精準配置，故不應就所附之圖式 的比例與配置關係解讀、侷限本發明於實際實施上的權利範圍，合先敘明。 The structure of the organochlorine selective film produced by the method of the present invention is as shown in Fig. 2. The drawings are used for the purpose of illustration and supplementary instructions, and are not necessarily true proportions and precise configurations after the implementation of the invention, and therefore should not be attached to the drawings. The relationship between the proportion and the configuration relationship is interpreted and the scope of the invention is actually stated in the actual implementation.
請參閱第2圖，其係為本發明有機氯選擇薄膜之結構圖。此圖中，本發明所述之有機氯選擇薄膜100包含玻璃碳電極層110、多壁奈米碳管層120以及電漿薄膜層130。多壁奈米碳管層120係設於玻璃碳電極層110上。電漿薄膜層130係設於多壁奈米碳管層120上。其中，多壁奈米碳管層120係利用電漿技術沉積於玻璃碳電極層110上，且利用電漿技術將電漿薄膜層130沉積於多壁奈米碳管層120上，以使玻璃碳電極層110進行電極修飾。而電漿薄膜層130之表面更可透過氨氣及四氟化碳之氣體進行表面改質，使得電漿薄膜層130之表面可具有符合有機氯農藥中之氯苯結構大小之複數個孔洞131。本發明所述之有機氯選擇薄膜，可應用於電化學農藥快速檢測，藉此選擇性地吸附有機氯農藥中之氯苯結構，以提升檢測有機氯農藥之偵測選擇性、再現性、靈敏度及偵測極限。 Please refer to Fig. 2, which is a structural diagram of the organochlorine selective film of the present invention. In the figure, the organochlorine selective film 100 of the present invention comprises a glassy carbon electrode layer 110, a multi-walled carbon nanotube layer 120, and a plasma film layer 130. The multi-walled carbon nanotube layer 120 is provided on the glassy carbon electrode layer 110. The plasma film layer 130 is provided on the multi-walled carbon nanotube layer 120. Wherein, the multi-walled carbon nanotube layer 120 is deposited on the glassy carbon electrode layer 110 by a plasma technique, and the plasma film layer 130 is deposited on the multi-walled carbon nanotube layer 120 by a plasma technique to make the glass The carbon electrode layer 110 is subjected to electrode modification. The surface of the plasma film layer 130 is further modified by a gas of ammonia gas and carbon tetrafluoride, so that the surface of the plasma film layer 130 can have a plurality of holes 131 conforming to the size of the chlorobenzene structure in the organochlorine pesticide. . The organochlorine selective film of the invention can be applied to the rapid detection of electrochemical pesticides, thereby selectively adsorbing the chlorobenzene structure in the organochlorine pesticide to improve the detection selectivity, reproducibility and sensitivity of the detection of organochlorine pesticides. And detection limits.
上述中，電漿薄膜層130可由高分子材料與氧化物所構成。而所述高分子材料可為三甲矽烷基氧化物(trimethylsilyl oxide,TMSO)以及含CF4或NH2基團之材料。以上僅係為舉例之實施態樣，但不應以此述而有所限制者。 In the above, the plasma film layer 130 may be composed of a polymer material and an oxide. The polymer material may be a trimethylsilyl oxide (TMSO) or a material containing a CF 4 or NH 2 group. The above is only an example of implementation, but should not be construed as limiting.
此外，本發明所製得之有機氯選擇薄膜係可應用於電化學農藥快速檢測之領域中，而所述電化學農藥分析方法，係於電化學反應環境中施加電位，使具有電化學活性之物質產生氧化或還原反應，同時即會有反應波峰產生，並由此反應波峰以判斷該反應是否為可逆反應。因此，本發明於預偵測有機氯農藥中之氯苯結構時，須先確認其在電化學反應中之氧化還原電位為何，故本發明在此係利用循環伏安法(Cyclic Voltammetry)之快速電位掃描特性所產生的波峰電位與波峰電流，進而 搜尋氯苯之氧化還原反應，如第3圖所示。由此結果可得知，有機氯農藥中之氯苯的氧化電位偵測條件，其係為依0.1~0.5V/S之速度施加高電位+3V~+5V、低電位-3V~-5V，以進行後續不同修飾電極之檢測。其中，較佳之氯苯的氧化電位偵測條件係為依0.5V/S之速度施加高電位+3.5V、低電位-3V，以偵測待側標的物是否殘留該有機氯農藥中之氯苯結構。 In addition, the organochlorine selective film prepared by the invention can be applied to the field of rapid detection of electrochemical pesticides, and the electrochemical pesticide analysis method applies an electric potential in an electrochemical reaction environment to make electrochemically active. The substance undergoes an oxidation or reduction reaction, and at the same time, a reaction peak is generated, and the peak is thereby reacted to determine whether the reaction is a reversible reaction. Therefore, in the present invention, when pre-detecting the chlorobenzene structure in the organochlorine pesticide, it is necessary to confirm the oxidation-reduction potential of the electrochemical reaction, so the present invention uses the rapid cyclization method (Cyclic Voltammetry). The peak potential and peak current generated by the potential sweep characteristic, and further Search for the redox reaction of chlorobenzene as shown in Figure 3. From this result, it can be known that the oxidation potential detection condition of chlorobenzene in the organochlorine pesticide is to apply a high potential of +3V to +5V and a low potential of -3V to -5V at a rate of 0.1 to 0.5 V/s. For subsequent detection of different modified electrodes. Among them, the preferred oxidative potential detection condition of chlorobenzene is to apply a high potential of +3.5 V and a low potential of -3 V at a rate of 0.5 V/S to detect whether the chlorobenzene in the organochlorine pesticide remains in the object to be flanked. structure.
更進一步地，係將本發明所製得之有機氯選擇薄膜進行有機氯農藥之靈敏度及偵測極限之偵測分析，請一併參閱第7圖及第8圖。第7圖係為本發明經電極活化處理及5次多壁奈米碳管修飾後之有機氯選擇薄膜相較未修飾玻璃碳電極以偵測有機氯農藥中之氯苯結構之電流之靈敏度分析圖。第8圖係為本發明經電極活化處理及5次多壁奈米碳管修飾後之有機氯選擇薄膜偵測不同濃度下之有機氯農藥中之氯苯結構之偵測極限分析圖。 Further, the organochlorine selective film prepared by the invention is subjected to detection and analysis of the sensitivity and detection limit of the organochlorine pesticide, and please refer to FIG. 7 and FIG. 8 together. Figure 7 is a sensitivity analysis of the current of the organochlorine selective film modified by the electrode activation treatment and the modified multi-walled carbon nanotubes to detect the chlorobenzene structure in the organochlorine pesticide. Figure. Fig. 8 is a graph showing the detection limit analysis of the chlorobenzene structure in the organochlorine pesticides at different concentrations after the electrode activation treatment and the five-wall multi-walled carbon nanotube modified organochlorine selective film.
第7圖中之(A)為經5次MWCNTs修飾的GCE電極，(B)為未修飾過之GCE電極，分別將兩種電極進行氯苯檢測之靈敏度分析，由結果可發現經5次MWCNTs修飾的GCE電極之電流波峰位於4.38A，而未修飾過之GCE電極之電流波峰為1.08A，將上述兩者相互比較可發現，GCE經5次修飾MWCNTs後其靈敏度有明顯上升，且上升有4倍之多。這可能是因為碳奈米表面上覆蓋的鏈條導電聚合物可加強導電的傳輸能力所致。此實驗可以證實MWCNTs/GCE修飾電極在電化學體系中，在針對有機氯農藥檢測上，是非常具前瞻性的一個開發平台。 In Fig. 7, (A) is a GCE electrode modified with 5 MWCNTs, and (B) is an unmodified GCE electrode. The sensitivity analysis of the two electrodes for chlorobenzene detection is performed, and 5 MWCNTs can be found from the results. The current peak of the modified GCE electrode is located at 4.38A, and the current peak of the unmodified GCE electrode is 1.08A. Comparing the two with each other, it can be found that the sensitivity of GCE after 5 modified MWCNTs is obviously increased, and the rise is 4 times as much. This may be due to the ability of the chain-coated conductive polymer covered on the surface of the carbon nanoparticle to enhance electrical conductivity. This experiment can confirm that MWCNTs/GCE modified electrode is a very forward-looking development platform for the detection of organochlorine pesticides in electrochemical systems.
而於不同濃度下之有機氯農藥之氯苯的偵測極限分析結果中，經NaOH電極活化且修飾5次多壁奈米碳管後之有機氯選擇薄膜相較未修飾玻璃碳電極，其所能達到之偵測極限濃度係為100ppb，如第8圖 所示，圖形標示處為氯苯濃度0.2ppm至0.1ppm時，能可看見清楚的氧化波峰，而濃度低於0.1ppm時，就無明顯的氧化波峰出現，因此判定本研究平台能針對濃度0.1ppm以上之有機氯農藥進行把關。 In the detection limit analysis results of chlorobenzene of organochlorine pesticides at different concentrations, the organochlorine selective film after activation by NaOH electrode and modified 5 times of multi-walled carbon nanotubes is compared with unmodified glassy carbon electrode. The detection limit concentration that can be achieved is 100ppb, as shown in Figure 8. As shown in the figure, when the concentration of the chlorobenzene is 0.2ppm to 0.1ppm, a clear oxidation peak can be seen, and when the concentration is less than 0.1ppm, no obvious oxidation peak appears. Therefore, the research platform can be determined to have a concentration of 0.1. Organochlorine pesticides above ppm are checked.
值得一提的是，本發明所述之有機氯選擇薄膜可應用於電化學農藥檢測領域中，以作為電化學農藥檢測平台中之工作電極4，如第9圖所示。藉由此概念可將作為工作電極4之有機氯選擇薄膜建構成攜帶型之微小感測器，便於農民、消費者或衛生單位使用，進而可將此技術提供至產業界，達到增廣應用之效益。其中，第9圖中所述之輔助電極2係作為輔助偵測氯苯之氧化還原電流之陽極，而參考電極5係作為偵測電流之校正電極。 It is worth mentioning that the organochlorine selective film of the present invention can be used in the field of electrochemical pesticide detection as the working electrode 4 in the electrochemical pesticide detection platform, as shown in FIG. By this concept, the organic chlorine selective film as the working electrode 4 can be constructed into a portable micro sensor for use by farmers, consumers or health units, and the technology can be provided to the industry for augmentation applications. benefit. Among them, the auxiliary electrode 2 described in FIG. 9 serves as an anode for detecting the redox current of chlorobenzene, and the reference electrode 5 serves as a correction electrode for detecting current.
綜合上述，本發明所述之有機氯選擇薄膜及其製備方法，其係利用電漿技術將多壁奈米碳管沉積於玻璃碳電極上，以形成多壁奈米碳管-玻璃碳修飾電極，再將經表面改質之電漿薄膜層沉積於所述多壁奈米碳管-玻璃碳修飾電極上，以形成具有選擇性偵測有機氯農藥中之氯苯結構的有機氯選擇薄膜。如此一來，本發明所述之有機氯選擇薄膜可應用於電化學農藥快速檢測之領域上，進而解決習知電化學農藥快速檢測方法中，其操作時間較長，且其對於待測標的物無較佳之選擇性，易受到干擾物影響而失去偵測之準確性，以及檢測效益不佳、再現性差、靈敏度低以及偵測極限有限之問題。 In summary, the organic chlorine selective film of the present invention and the preparation method thereof are characterized in that a multi-walled carbon nanotube is deposited on a glassy carbon electrode by a plasma technique to form a multi-walled carbon nanotube-glassy carbon modified electrode. Then, a surface-modified plasma film layer is deposited on the multi-walled carbon nanotube-glassy carbon modified electrode to form an organic chlorine selective film having a structure for selectively detecting a chlorobenzene structure in the organochlorine pesticide. In this way, the organochlorine selective film of the present invention can be applied to the field of rapid detection of electrochemical pesticides, thereby solving the conventional rapid detection method of electrochemical pesticides, which has a long operation time and is suitable for the object to be tested. There is no better selectivity, it is susceptible to interference and the accuracy of detection is lost, and the detection efficiency is poor, the reproducibility is poor, the sensitivity is low, and the detection limit is limited.
以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中。 The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the invention are intended to be included in the scope of the appended claims.
S11~S15‧‧‧步驟 S11~S15‧‧‧Steps
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