TWI677472B - Detection method for heavy metal ions - Google Patents
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Abstract
提出一種重金屬離子的檢測方法，其包括下列步驟。使廢水流經用以吸附至少兩種目標金屬離子的離子拓印高分子管。沖洗離子拓印高分子管，以移除離子拓印高分子管中的非目標物。以酸液脫附離子拓印高分子管中的目標金屬離子。以電化學法檢測目標金屬離子的濃度。A method for detecting heavy metal ions is proposed, which includes the following steps. The wastewater is passed through an ion-imprinted polymer tube for adsorbing at least two kinds of target metal ions. Rinse the ion-imprinted polymer tube to remove non-targets from the ion-imprinted polymer tube. The target metal ions in the polymer tube are imprinted with acid desorption ions. The concentration of the target metal ion is detected electrochemically.
Description
本發明是有關於一種重金屬離子的檢測方法，且是有關於一種檢測廢水中的重金屬離子的檢測方法。The invention relates to a method for detecting heavy metal ions, and to a method for detecting heavy metal ions in wastewater.
近年來，由於工業如電鍍、光電、印刷電路板及半導體產業快速發展，造成日益嚴重的重金屬廢水污染問題。重金屬廢水不僅會對人體造成嚴重的傷害，還會破壞人類生存的環境，因此廢水中的重金屬離子的檢測方法變得相當重要。然而，未處理的廢水中具有基質，其會干擾造成檢測出來的訊號偏移及抑制，使定性及定量的檢測結果的準確度下降。因此在檢測前，必須先對廢水進行處理。In recent years, due to the rapid development of industries such as electroplating, optoelectronics, printed circuit boards and semiconductor industries, the problem of heavy metal wastewater pollution has become increasingly serious. Heavy metal wastewater not only causes serious harm to the human body, but also destroys the environment in which humans live. Therefore, the detection method of heavy metal ions in wastewater becomes very important. However, there is a matrix in the untreated wastewater, which will cause the detected signal to shift and suppress, which will reduce the accuracy of the qualitative and quantitative detection results. Therefore, the wastewater must be treated before testing.
一般而言，會藉由稀釋或標準添加法，將基質的影響降低，但若目標金屬離子的濃度很低，則檢測結果會不準確。另一方式是將電極進行修飾來降低電位偏移。然而，修飾電極的價位高，且針對不同目標金屬離子需要不同修飾電極，導致高成本以及更多處理步驟。In general, the influence of the matrix is reduced by dilution or standard addition methods, but if the concentration of the target metal ion is very low, the detection result will be inaccurate. Another way is to modify the electrodes to reduce the potential shift. However, the price of modified electrodes is high, and different modified electrodes are required for different target metal ions, resulting in high cost and more processing steps.
本發明提供一種重金屬離子的檢測方法，可以解決廢水的基質所造成的訊號偏移及抑制的問題，以提升定性及定量的檢測結果的準確度。The invention provides a method for detecting heavy metal ions, which can solve the problem of signal shift and suppression caused by the matrix of wastewater, so as to improve the accuracy of qualitative and quantitative detection results.
本發明的一種重金屬離子的檢測方法包括下列步驟。使廢水流經用以吸附至少兩種目標金屬離子的離子拓印高分子管。沖洗離子拓印高分子管，以移除離子拓印高分子管中的非目標物。以酸液脫附離子拓印高分子管中的目標金屬離子。以電化學法檢測目標金屬離子的濃度。A method for detecting heavy metal ions of the present invention includes the following steps. The wastewater is passed through an ion-imprinted polymer tube for adsorbing at least two kinds of target metal ions. Rinse the ion-imprinted polymer tube to remove non-targets from the ion-imprinted polymer tube. The target metal ions in the polymer tube are imprinted with acid desorption ions. The concentration of the target metal ion is detected electrochemically.
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.
圖1為本發明一實施例的重金屬離子的檢測方法的流程圖。圖2為本發明一實施例的重金屬離子的檢測方法的操作示意圖。FIG. 1 is a flowchart of a method for detecting heavy metal ions according to an embodiment of the present invention. FIG. 2 is an operation schematic diagram of a method for detecting heavy metal ions according to an embodiment of the present invention.
請同時參照圖1及圖2的(a)，進行步驟S100，使廢水100流經用以吸附至少兩種目標金屬離子102的離子拓印高分子管104。廢水100具有目標金屬離子102及非目標物103。在一實施例中，目標金屬離子102包括第一目標金屬離子102a及第二目標金屬離子102b，但本發明不限於此。在另一實施例中，目標金屬離子102也可包括三種或多於三種的目標金屬離子。Referring to FIG. 1 and FIG. 2 (a) at the same time, step S100 is performed to make the wastewater 100 flow through the ion-imprinted polymer tube 104 for adsorbing at least two kinds of target metal ions 102. The wastewater 100 includes a target metal ion 102 and a non-target object 103. In one embodiment, the target metal ion 102 includes a first target metal ion 102a and a second target metal ion 102b, but the present invention is not limited thereto. In another embodiment, the target metal ion 102 may also include three or more than three target metal ions.
此外，目標金屬離子102包括鉛離子、銅離子、鉻離子、鎳離子、鋅離子及鎘離子中的至少兩者。目標金屬離子102也可以是其他常見於廢水100中的金屬離子。非目標物103即為廢水100的基質。非目標物103包括非目標金屬離子、有機物、導電性雜質、干擾物或其組合，但本發明不限於此。The target metal ion 102 includes at least two of a lead ion, a copper ion, a chromium ion, a nickel ion, a zinc ion, and a cadmium ion. The target metal ion 102 may also be other metal ions commonly used in wastewater 100. The non-target object 103 is the matrix of the wastewater 100. The non-target object 103 includes non-target metal ions, organic substances, conductive impurities, interference substances, or a combination thereof, but the present invention is not limited thereto.
在一實施例中，廢水100的導電度大於或等於約2,000微西門子/公分。更詳細地說，廢水100的導電度例如是介於約2,000微西門子/公分至3,000微西門子/公分之間。當使用剝除伏安法量測廢水中的金屬離子濃度時，其波峰位置與強度會受到廢水的導電度值嚴重影響，造成訊號偏移及變形，使定性及定量的檢測出現誤判。In one embodiment, the conductivity of the wastewater 100 is greater than or equal to about 2,000 microSiemens / cm. In more detail, the conductivity of the wastewater 100 is, for example, between about 2,000 micro-Siemens / cm to 3,000 micro-Siemens / cm. When stripping voltammetry is used to measure the concentration of metal ions in wastewater, its peak position and intensity will be severely affected by the conductivity value of the wastewater, causing signal shifts and deformations, which will cause qualitative and quantitative detection to be misjudged.
在一實施例中，離子拓印高分子管104具有至少兩種離子拓印高分子106，用以吸附至少兩種目標金屬離子102。在一實施例中，離子拓印高分子106包括第一離子拓印高分子106a及第二離子拓印高分子106b。第一離子拓印高分子106a及第二離子拓印高分子106b例如是與矽砂均勻混合後，填充於離子拓印高分子管104。在一實施例中，離子拓印高分子管104也可具有三種或多於三種的離子拓印高分子，用以吸附三種或多於三種的目標金屬離子。In one embodiment, the ion-imprinted polymer tube 104 has at least two kinds of ion-imprinted polymers 106 for adsorbing at least two kinds of target metal ions 102. In one embodiment, the ion-imprinted polymer 106 includes a first ion-imprinted polymer 106a and a second ion-imprinted polymer 106b. The first ion-imprinted polymer 106a and the second ion-imprinted polymer 106b are, for example, uniformly mixed with silica sand and then filled in the ion-imprinted polymer tube 104. In an embodiment, the ion-imprinted polymer tube 104 may also have three or more than three ion-imprinted polymers for adsorbing three or more target metal ions.
離子拓印高分子106的製造方法如下，先提供模板分子，再提供官能基單體與模板分子產生鍵結。然後，加入交聯劑進行聚合反應產生聚合高分子，再將模板分子從聚合高分子內移除，以得到具有孔洞的離子拓印高分子106，且孔洞表面上具有官能基。The manufacturing method of the ion-imprinted polymer 106 is as follows. First, a template molecule is provided, and then a functional group monomer is provided to generate a bond with the template molecule. Then, a cross-linking agent is added to perform a polymerization reaction to generate a polymer, and then the template molecule is removed from the polymer to obtain an ion-imprinted polymer 106 having a hole, and the surface of the hole has a functional group.
由於離子拓印高分子106的孔洞結構與其原先鍵結的模板分子的結構相同，所以孔洞可捕捉與模板分子的結構相似的目標金屬離子102。之後，離子拓印高分子106會與被孔洞所捕捉的目標金屬離子102產生鍵結，以固定目標金屬離子102。因此，離子拓印高分子106具有辨識特定目標且吸附該特定目標的高選擇性，所以不同種類的離子拓印高分子106可以吸附不同種類的目標金屬離子102。Because the pore structure of the ion-imprinted polymer 106 is the same as the structure of the template molecule to which it was originally bonded, the pores can capture the target metal ion 102 similar to the structure of the template molecule. After that, the ion-imprinted polymer 106 will bond with the target metal ion 102 captured by the hole to fix the target metal ion 102. Therefore, the ion-imprinted polymer 106 has a high selectivity in identifying a specific target and adsorbing the specific target, so different types of ion-imprinted polymers 106 can adsorb different kinds of target metal ions 102.
在一實施例中，第一離子拓印高分子106a與第二離子拓印高分子106b的孔洞具有不同的結構，因此第一離子拓印高分子106a與第二離子拓印高分子106b會吸附不同種類的目標金屬離子102。此外，由於離子拓印高分子106的孔洞的結構與非目標物103的結構不同，因此離子拓印高分子106不會吸附非目標物103。In an embodiment, the pores of the first ion-imprinted polymer 106a and the second ion-imprinted polymer 106b have different structures, so the first ion-imprinted polymer 106a and the second ion-imprinted polymer 106b will adsorb. Different kinds of target metal ions 102. In addition, since the structure of the pores of the ion-imprinted polymer 106 is different from the structure of the non-target object 103, the ion-imprinted polymer 106 does not adsorb the non-target object 103.
值得注意的是，廢水100中不同種類的目標金屬離子102同時被離子拓印高分子管104吸附，且目標金屬離子102是在單一個離子拓印高分子管104中被吸附。因此，本發明無需使用超過一個的離子拓印高分子管104來吸附目標金屬離子102，藉此節省檢測步驟以及成本。It is worth noting that different kinds of target metal ions 102 in the wastewater 100 are simultaneously adsorbed by the ion-imprinted polymer tube 104, and the target metal ions 102 are adsorbed in a single ion-imprinted polymer tube 104. Therefore, the present invention does not need to use more than one ion-imprinted polymer tube 104 to adsorb the target metal ions 102, thereby saving detection steps and costs.
然後，請同時參照圖1及圖2的(b)，進行步驟S200，沖洗離子拓印高分子管104，以移除離子拓印高分子管104中的非目標物103。更詳細地說，離子拓印高分子106與目標金屬離子102之間具有鍵結，所以目標金屬離子102被離子拓印高分子106吸附而不會被沖洗出離子拓印高分子管104。非目標物103沒有被離子拓印高分子106吸附，所以當沖洗離子拓印高分子管104時，非目標物103會流出離子拓印高分子管104。Then, referring to FIG. 1 and FIG. 2 (b) simultaneously, step S200 is performed to rinse the ion-imprinted polymer tube 104 to remove the non-target object 103 in the ion-imprinted polymer tube 104. In more detail, there is a bond between the ion-imprinted polymer 106 and the target metal ion 102, so the target metal ion 102 is adsorbed by the ion-imprinted polymer 106 without being washed out of the ion-imprinted polymer tube 104. The non-target object 103 is not adsorbed by the ion-imprinted polymer 106, so when the ion-imprinted polymer tube 104 is rinsed, the non-target object 103 will flow out of the ion-imprinted polymer tube 104.
在一實施例中，使用去離子水108來沖洗離子拓印高分子管104，但本發明不限於此。在一實施例中，使用緩衝液或有機溶液來沖洗離子拓印高分子管104。緩衝液包括醋酸/醋酸鈉、鹽酸、磷酸硼酸混和溶液（Britton-Robinso）、銨/氯化銨、磷酸、類似物或其組合，有機溶劑則可選用甲醇、乙醇、類似物或其組合。此外，只要是具有良好的流動性並且不會破壞離子拓印高分子106與目標金屬離子102之間的鍵結的液體，都適用於沖洗離子拓印高分子管104。In one embodiment, the ion-imprinted polymer tube 104 is rinsed with deionized water 108, but the present invention is not limited thereto. In one embodiment, a buffer solution or an organic solution is used to rinse the ion-imprinted polymer tube 104. The buffer solution includes acetic acid / sodium acetate, hydrochloric acid, phosphoric acid boric acid mixed solution (Britton-Robinso), ammonium / ammonium chloride, phosphoric acid, the like, or a combination thereof, and the organic solvent may be methanol, ethanol, the like, or a combination thereof. In addition, as long as it is a liquid that has good fluidity and does not break the bond between the ion-imprinted polymer 106 and the target metal ion 102, it is suitable for flushing the ion-imprinted polymer tube 104.
之後，請同時參照圖1及圖2的(c)，進行步驟S300，以酸液110脫附離子拓印高分子管104中的目標金屬離子102。更詳細地說，酸液110會弱化離子拓印高分子106與目標金屬離子102之間的鍵結，導致離子拓印高分子106無法繼續吸附目標金屬離子102。此外，當酸液110的酸鹼值（pH值）越小，酸度愈強時，酸液110弱化鍵結的效果愈好。酸液110的酸鹼值例如是小於或等於5，例如介於0至5之間。酸液110包括硫酸、鹽酸、硝酸或其組合，但本發明不限於此。鹽酸例如是pH值為2的鹽酸。此外，其他可用來弱化離子拓印高分子106與目標金屬離子102之間的鍵結的化合物亦適用於本發明。Thereafter, referring to FIG. 1 and FIG. 2 (c) at the same time, step S300 is performed, and the target metal ion 102 in the polymer tube 104 is desorbed by the acid solution 110. In more detail, the acid solution 110 weakens the bond between the ion-imprinted polymer 106 and the target metal ion 102, so that the ion-imprinted polymer 106 cannot continue to adsorb the target metal ion 102. In addition, the smaller the acid-base value (pH value) of the acid solution 110 and the stronger the acidity, the better the effect of the acid solution 110 to weaken the bonding. The acid-base value of the acid solution 110 is, for example, less than or equal to 5, for example, between 0 and 5. The acid solution 110 includes sulfuric acid, hydrochloric acid, nitric acid, or a combination thereof, but the present invention is not limited thereto. The hydrochloric acid is, for example, hydrochloric acid having a pH of 2. In addition, other compounds that can be used to weaken the bond between the ion-imprinted polymer 106 and the target metal ion 102 are also suitable for the present invention.
另外，將目標金屬離子102脫附後，可以對離子拓印高分子管104進行乾燥處理，即可再次用來吸附目標金屬離子102，以達到節省成本的效果。In addition, after the target metal ion 102 is desorbed, the ion-imprinted polymer tube 104 can be dried, and can be used to adsorb the target metal ion 102 again, so as to achieve a cost-saving effect.
接著，請同時參照圖1及圖2的(d)，進行步驟S400，以電化學法檢測目標金屬離子102的濃度。詳細地說，在酸液110脫附目標金屬離子102後，將包含目標金屬離子102的酸液110流至檢測容器112，如圖3所示。然後，以電化學法檢測目標金屬離子102的濃度。在一實施例中，所使用的電化學法為陽極剝除伏安法（anodic stripping voltammetry，ASV）。此外，在特殊情形下（如，濃度適中，且已定性），則可以單純使用循環伏安法。Next, referring to FIG. 1 and FIG. 2 (d) simultaneously, step S400 is performed to detect the concentration of the target metal ion 102 electrochemically. In detail, after the target metal ion 102 is desorbed by the acid liquid 110, the acid liquid 110 containing the target metal ion 102 is flowed to the detection container 112, as shown in FIG. 3. Then, the concentration of the target metal ion 102 is detected electrochemically. In one embodiment, the electrochemical method used is anodic stripping voltammetry (ASV). In addition, in special cases (such as moderate concentrations and qualitative), cyclic voltammetry can be used simply.
在一實施例中，陽極剝除伏安法是使用網版印刷三極式電極板114來檢測目標金屬離子102的濃度，網版印刷三極式電極板114的裝置示意圖如圖3的(a)所示。網版印刷三極式電極板114的體積很小，因此具有攜帶方便的優點。In one embodiment, the anode stripping voltammetry method uses a screen-printed tripolar electrode plate 114 to detect the concentration of the target metal ion 102. The schematic diagram of the device for the screen-printed tripolar electrode plate 114 is shown in FIG. 3 (a ). The screen printing tripolar electrode plate 114 has a small volume, and therefore has the advantage of being convenient to carry.
接著，請參照圖3的(a)，網版印刷三極式電極板114具有工作電極（working electrode）116、輔助電極（counter electrode）118以及參考電極（reference electrode）120。工作電極116的材料包括金或鉍。輔助電極118的材料包括金、白金或碳。參考電極120的材料包括氯化銀或銀。此外，網版印刷三極式電極板114更具有工作電極傳輸部122（電性連接至工作電極116）、輔助電極傳輸部124（電性連接至輔助電極118）以及參考電極傳輸部126（電性連接至參考電極120），能夠將測得的訊號輸出至訊號分析裝置（未繪示），以製作出電位-電流圖。Next, referring to FIG. 3 (a), the screen-printed tripolar electrode plate 114 includes a working electrode 116, a counter electrode 118, and a reference electrode 120. The material of the working electrode 116 includes gold or bismuth. The material of the auxiliary electrode 118 includes gold, platinum, or carbon. The material of the reference electrode 120 includes silver chloride or silver. In addition, the screen-printed tripolar electrode plate 114 further includes a working electrode transmission portion 122 (electrically connected to the working electrode 116), an auxiliary electrode transmission portion 124 (electrically connected to the auxiliary electrode 118), and a reference electrode transmission portion 126 (electrical It is connected to the reference electrode 120) to output the measured signal to a signal analysis device (not shown) to make a potential-current diagram.
在使用網版印刷三極式電極板114來檢測目標金屬離子102的濃度時，工作電極116、輔助電極118以及參考電極120會浸泡於包含目標金屬離子102的酸液110中，以檢測目標金屬離子102的濃度。當參考電極120的材料包括銀時，且酸液110的pH值小於2時，酸液110會嚴重腐蝕參考電極120，導致網版印刷三極式電極板114的檢測功能失效。When using a screen-printed tripolar electrode plate 114 to detect the concentration of the target metal ion 102, the working electrode 116, the auxiliary electrode 118, and the reference electrode 120 are immersed in an acid solution 110 containing the target metal ion 102 to detect the target metal. The concentration of ions 102. When the material of the reference electrode 120 includes silver and the pH value of the acid solution 110 is less than 2, the acid solution 110 will severely corrode the reference electrode 120, causing the detection function of the screen-printed tripolar electrode plate 114 to fail.
因此為了避免酸液110嚴重腐蝕包括銀的參考電極120，並且還能有效地脫附目標金屬離子102，酸液110較佳的pH值範圍介於2至5之間。如此，可以使目標金屬離子102能夠弱化離子拓印高分子106與目標金屬離子102之間的鍵結，且能維持參考電極120的運作。Therefore, in order to prevent the acid solution 110 from seriously corroding the reference electrode 120 including silver, and also to effectively desorb the target metal ion 102, the preferred pH range of the acid solution 110 is between 2 and 5. In this way, the target metal ion 102 can be made to weaken the bond between the ion-imprinted polymer 106 and the target metal ion 102, and the operation of the reference electrode 120 can be maintained.
在另一實施例中，陽極剝除伏安法例如是使用三極式電極棒128來檢測目標金屬離子102的濃度，三極式電極棒128的裝置示意圖如圖3的(b)所示。三極式電極棒128具有工作電極130、輔助電極132以及參考電極134，工作電極130的材料包括金或鉍。輔助電極132的材料包括金或碳。參考電極134的材料包括氯化銀或銀。In another embodiment, the anodic stripping voltammetry method uses, for example, a tripolar electrode rod 128 to detect the concentration of the target metal ion 102. A schematic diagram of the device of the tripolar electrode rod 128 is shown in FIG. 3 (b). The tripolar electrode rod 128 has a working electrode 130, an auxiliary electrode 132, and a reference electrode 134. The material of the working electrode 130 includes gold or bismuth. The material of the auxiliary electrode 132 includes gold or carbon. The material of the reference electrode 134 includes silver chloride or silver.
在使用三極式電極棒128來檢測目標金屬離子102的濃度時，工作電極130、輔助電極132以及參考電極134會浸泡於包含目標金屬離子102的酸液110，以檢測目標金屬離子102的濃度，製作出電位-電流圖。When the tri-electrode electrode rod 128 is used to detect the concentration of the target metal ion 102, the working electrode 130, the auxiliary electrode 132, and the reference electrode 134 are immersed in the acid solution 110 containing the target metal ion 102 to detect the concentration of the target metal ion 102. To make a potential-current diagram.
值得注意的是，三極式電極棒128的輔助電極132及參考電極134的大部分的表面由玻璃136所包覆。因此當參考電極134的材料包括銀時，玻璃136可以保護大部分的參考電極134不被酸液110腐蝕。所以，相較於使用網版印刷三極式電極板114，可以選擇使用酸度更強的酸液110，以達到更有效脫附目標金屬離子102的效果且不會破壞參考電極134。酸液110的pH值例如是介於0至5之間。It is worth noting that most of the surfaces of the auxiliary electrode 132 and the reference electrode 134 of the tripolar electrode rod 128 are covered with glass 136. Therefore, when the material of the reference electrode 134 includes silver, the glass 136 can protect most of the reference electrode 134 from being corroded by the acid solution 110. Therefore, rather than using a screen-printed tripolar electrode plate 114, an acid solution 110 having a stronger acidity can be selected to achieve a more effective desorption of the target metal ion 102 without damaging the reference electrode 134. The pH of the acid solution 110 is, for example, between 0 and 5.
習知的重金屬離子的檢測方法會使用電極修飾來減少非目標物103對檢測結果的影響，但電極修飾具有成本高的缺點。相較於使用習知的電極修飾的方法進行檢測，本發明的重金屬離子的檢測方法可以直接使用不經電極修飾的工作電極116/130、輔助電極118/132及參考電極120/134來對目標金屬離子102進行濃度的檢測，藉此達到節省成本的效果。Conventional methods for detecting heavy metal ions use electrode modification to reduce the effect of non-targets 103 on the detection results, but electrode modification has the disadvantage of high cost. Compared with the conventional electrode modification method for detection, the method for detecting heavy metal ions of the present invention can directly use the working electrode 116/130, auxiliary electrode 118/132, and reference electrode 120/134 without electrode modification to target The concentration of the metal ions 102 is detected, thereby achieving a cost-saving effect.
此外，本發明的方法中，以電化學法檢測目標金屬離子的濃度之前，廢水的干擾基質已全部被置換為酸液110。以此方式，能有效降低干擾，讓目標金屬離子的氧化電位與純水系統維持一致，有效降低誤判。此外，本發明能將任何原水中之基質，置換成固定濃度的酸液，此舉能有效延長電極之使用壽命。In addition, in the method of the present invention, before the concentration of the target metal ion is detected by the electrochemical method, the interference matrix of the wastewater has been completely replaced with the acid solution 110. In this way, interference can be effectively reduced, the oxidation potential of the target metal ion can be kept consistent with the pure water system, and false judgments can be effectively reduced. In addition, the invention can replace the substrate in any raw water with an acid solution with a fixed concentration, which can effectively extend the service life of the electrode.
另外，在本發明的方法中，以電化學法檢測目標金屬離子102的濃度之前，由於會干擾檢測的非目標物103已被移除，因此可避免在檢測目標物的濃度時非目標物造成的干擾，進而得到較準確的檢測結果。更具體地說，由於非目標物103干擾檢測結果的問題已經改善，所以透過本發明的方法檢測低濃度的目標金屬離子102，能夠檢測到其原本被抑制的低強度訊號。本發明的檢測方法能檢測到目標金屬離子102的濃度例如是等於或小於15 ppm、10 ppm、5 ppm或2 ppm。In addition, in the method of the present invention, before the concentration of the target metal ion 102 is detected by an electrochemical method, the non-target object 103 that would interfere with the detection has been removed, so that the non-target object can be avoided when the concentration of the target object is detected. Interference in order to obtain more accurate detection results. More specifically, since the problem that the non-target object 103 interferes with the detection result has been improved, by detecting the low-concentration target metal ion 102 through the method of the present invention, a low-intensity signal that is originally suppressed can be detected. The detection method of the present invention can detect that the concentration of the target metal ion 102 is, for example, 15 ppm, 10 ppm, 5 ppm, or 2 ppm.
再者，本發明的酸液110脫附離子拓印高分子管104中的目標金屬離子102之後，不需要對目標金屬離子102進行再處理，即可立即對目標金屬離子102進行檢測。如此，能達到節省檢測步驟的效果。Furthermore, after the target metal ion 102 in the ion-imprinted polymer tube 104 is desorbed by the acid solution 110 of the present invention, the target metal ion 102 can be detected immediately without reprocessing the target metal ion 102. In this way, the effect of saving detection steps can be achieved.
以下，提供多個實驗例與比較例來說明上述實施例的功效，但本發明的範圍並不侷限於以下內容。In the following, a plurality of experimental examples and comparative examples are provided to explain the effects of the above embodiments, but the scope of the present invention is not limited to the following.
＜實驗例1＞＜ Experimental Example 1 ＞
提供廢水，其pH值大約為6，而導電度大約為2,000微西門子/公分。接著，添加2 ppm的銅離子至廢水。之後，使廢水流經具有銅離子拓印高分子的離子拓印高分子管，以對銅離子進行吸附。Wastewater is provided with a pH of approximately 6 and a conductivity of approximately 2,000 microSiemens / cm. Next, 2 ppm of copper ions were added to the wastewater. After that, the wastewater is passed through an ion-imprinted polymer tube having a copper-ion imprinted polymer to adsorb copper ions.
銅離子拓印高分子詳細製備方式如下，將4 mmole的4-乙烯基吡啶（4-vinyl pyridine）（作為官能基單體）和0.5 mmole的硝酸銅（Cu(NO3 )2 ）（作為模板離子）加入35 ml的乙腈中攪拌過夜。再取20 mmole的二甲基丙烯酸乙二醇酯（EGDMA）（作為交聯劑）加入溶液中，將溶液通入N2 去除溶液中的O2 ，將溶液置於65℃油浴中，再加入100 mg的偶氮二異丁腈（AIBN）（作為起始劑）於溶液中攪拌反應24小時。待其反應完成後，將產生之粉體先以體積比為1:4的甲醇/水清洗數次，去除未反應之物質，再以0.5M HCl清洗粉體數次，將粉體中之Cu2+ 去除，最後以去離子水清洗直到粉體達中性，將粉體置於烘箱中烘乾。之後進行研磨後即可得到銅離子拓印高分子。The detailed preparation method of copper ion imprinted polymer is as follows. 4 mmole of 4-vinyl pyridine (as a functional monomer) and 0.5 mmole of copper nitrate (Cu (NO 3 ) 2 ) (as a template) Ion) was added to 35 ml of acetonitrile and stirred overnight. Another 20 mmole of ethylene glycol dimethacrylate (EGDMA) (as a cross-linking agent) was added to the solution, and the solution was passed into N 2 to remove O 2 from the solution. The solution was placed in a 65 ° C oil bath, and then Add 100 mg of azobisisobutyronitrile (AIBN) (as a starter) to the solution and stir for 24 hours. After the reaction is completed, the generated powder is washed several times with methanol / water with a volume ratio of 1: 4 to remove unreacted materials, and then the powder is washed several times with 0.5M HCl to remove the Cu in the powder. 2+ is removed, and finally the powder is washed with deionized water until the powder becomes neutral, and the powder is dried in an oven. After grinding, a copper ion imprinted polymer can be obtained.
接著，使用去離子水對離子拓印高分子管進行沖洗，去除基質。然後，使用pH值大約為2的鹽酸脫附銅離子。最後，使用網版印刷三極式電極板對具有銅離子的鹽酸進行陽極剝除伏安法檢測，其結果如圖4的曲線1所示。Next, the ion-imprinted polymer tube is rinsed with deionized water to remove the matrix. Then, copper ion was desorbed using hydrochloric acid having a pH of about 2. Finally, anodic stripping voltammetry was performed on hydrochloric acid with copper ions using a screen-printed tripolar electrode plate. The results are shown in curve 1 in FIG. 4.
＜比較例1＞〈Comparative example 1〉
提供與實驗例1相同的廢水。接著，添加2 ppm的銅離子至廢水。之後，直接使用網版印刷三極式電極板來對廢水進行陽極剝除伏安法檢測，其結果如圖4的曲線2所示。The same wastewater as in Experimental Example 1 was provided. Next, 2 ppm of copper ions were added to the wastewater. After that, the screen printing tripolar electrode plate was directly used to perform anodic stripping voltammetry on the wastewater, and the result is shown in curve 2 in FIG. 4.
＜比較例2＞〈Comparative example 2〉
提供去離子水。添加2 ppm的銅離子至去離子水。之後，直接使用網版印刷三極式電極板來對去離子水進行陽極剝除伏安法檢測，其結果如圖4的曲線3所示。Provide deionized water. Add 2 ppm of copper ions to deionized water. After that, the screen printing tripolar electrode plate was directly used for anodic stripping voltammetry detection of deionized water, and the result is shown in curve 3 in FIG. 4.
比較圖4的曲線1、曲線2及曲線3，可知經實驗例1所檢測的電位及電流訊號與比較例2的檢測結果很接近，反觀經比較例1所檢測的電位及電流訊號相較於比較例2的檢測結果偏移很多。由此說明經由本發明的重金屬離子的檢測方法，能夠得到較準確的定量及定性分析。Comparing curve 1, curve 2 and curve 3 in FIG. 4, it can be seen that the potential and current signals detected by Experimental Example 1 are very close to the detection results of Comparative Example 2. In contrast, the potential and current signals detected by Comparative Example 1 are compared with The detection result of Comparative Example 2 is greatly shifted. This shows that through the method for detecting heavy metal ions of the present invention, a more accurate quantitative and qualitative analysis can be obtained.
此外，將經實驗例1、比較例1及比較例2所測得的銅離子的濃度記錄於表1。此外，另外將實驗例1、比較例1及比較例2的陽極剝除伏安法更改為使用原子吸收光譜法（atomic absorption spectroscopy，AAS），以原子吸收光譜儀來檢測銅離子的濃度，其結果亦記錄於表1。In addition, the copper ion concentrations measured in Experimental Example 1, Comparative Example 1, and Comparative Example 2 are recorded in Table 1. In addition, the anode stripping voltammetry of Experimental Example 1, Comparative Example 1, and Comparative Example 2 was changed to use atomic absorption spectroscopy (AAS) to detect the concentration of copper ions with an atomic absorption spectrometer. The results were Also recorded in Table 1.
表1
根據表1，可知實驗例1中，經本發明的吸附、沖洗及脫附處理後再使用陽極剝除伏安法所測得的銅離子濃度，相較於比較例1中直接以陽極剝除伏安法對含有2 ppm銅離子的未處理廢水檢測所得的濃度，更接近銅離子的實際濃度。此外，比較例1相較於實驗例1，具有較大的誤差值，可知經本發明的重金屬離子的檢測方法，可以改善基質造成的訊號偏移及抑制，並且可以提升定性及定量的檢測結果的準確度。According to Table 1, it can be seen that in Experimental Example 1, the copper ion concentration measured by the anodic stripping voltammetry after the adsorption, rinsing, and desorption treatments of the present invention is compared with the anodic stripping of volts directly in Comparative Example 1. The concentration measured by Anfa for untreated wastewater containing 2 ppm copper ions is closer to the actual concentration of copper ions. In addition, Comparative Example 1 has a larger error value than Experimental Example 1. It can be seen that the method for detecting heavy metal ions according to the present invention can improve the signal shift and suppression caused by the matrix, and can improve the qualitative and quantitative detection results. Accuracy.
＜實驗例2＞＜ Experimental Example 2 ＞
提供廢水，其pH值大約為6，而導電度大約為2,000微西門子/公分。接著，添加2 ppm的鉛離子至廢水。之後，使廢水流經具有鉛離子拓印高分子的離子拓印高分子管，以對鉛離子進行吸附。Wastewater is provided with a pH of approximately 6 and a conductivity of approximately 2,000 microSiemens / cm. Next, 2 ppm of lead ions were added to the wastewater. After that, the wastewater is passed through an ion-imprinted polymer tube having a lead-ion imprinted polymer to adsorb lead ions.
鉛離子拓印高分子詳細製備方式如下，將0.89 g的1-乙烯咪唑（1-vinylimidazole）和0.0828 g的硝酸鉛Pb(NO3 )2 加入5 ml的四氫呋喃（Tetrahydrofuran，THF）攪拌30分鐘。再取0.13 g的3-（三甲氧基矽烷基）丙基甲基丙烯酸酯（3-(trimethoxysilyl) propylmethacrylate，TMSPMA）和2 ml的四氫呋喃加入溶液中，將溶液通入N2 去除溶液中的O2 ，將溶液置於68℃油浴中，再加入1.6 mg的AIBN於溶液中攪拌反應16小時。待其反應完成後，將產生之粉體先以2M硝酸清洗數次，將粉體中之Pb2+ 去除，最後以去離子水清洗直到粉體達中性，將粉體置於烘箱中烘乾。待研磨後即可得當產物。The detailed preparation method of lead ion imprinted polymer is as follows. 0.89 g of 1-vinylimidazole and 0.0828 g of lead nitrate Pb (NO 3 ) 2 are added to 5 ml of tetrahydrofuran (Tetrahydrofuran, THF) and stirred for 30 minutes. Then, 0.13 g of 3- (trimethoxysilyl) propylmethacrylate (TMSPMA) and 2 ml of tetrahydrofuran were added to the solution, and the solution was passed into N 2 to remove O in the solution. 2. Place the solution in a 68 ° C oil bath, add 1.6 mg of AIBN, and stir the solution for 16 hours. After the reaction is completed, the generated powder is washed several times with 2M nitric acid to remove the Pb 2+ in the powder, and finally washed with deionized water until the powder is neutral, and the powder is dried in an oven. dry. After grinding, the product can be obtained.
接著，使用去離子水對離子拓印高分子管進行沖洗，去除基質。然後，使用pH值大約為2的鹽酸脫附鉛離子。最後，使用網版印刷三極式電極板對具有鉛離子的鹽酸進行陽極剝除伏安法檢測。Next, the ion-imprinted polymer tube is rinsed with deionized water to remove the matrix. Then, hydrochloric acid having a pH of about 2 was used to desorb the lead ions. Finally, anodic stripping voltammetry was performed on the hydrochloric acid with lead ions using a screen-printed tripolar electrode plate.
＜比較例3＞〈Comparative example 3〉
提供與實驗例2相同的廢水。接著，添加2 ppm的鉛離子至廢水。之後，直接使用網版印刷三極式電極板來對廢水進行陽極剝除伏安法檢測。The same wastewater as in Experimental Example 2 was provided. Next, 2 ppm of lead ions were added to the wastewater. After that, the screen printing tripolar electrode plate was directly used for anodic stripping voltammetry detection of wastewater.
＜比較例4＞〈Comparative example 4〉
提供去離子水。添加2 ppm的鉛離子至去離子水。之後，直接使用網版印刷三極式電極板來對去離子水進行陽極剝除伏安法檢測。Provide deionized water. Add 2 ppm of lead ions to deionized water. After that, the screen printing tripolar electrode plate was directly used for anodic stripping voltammetry detection of deionized water.
此外，將經實驗例2、比較例3及比較例4所測得的鉛離子的濃度記錄於表2。並再將實驗例2、比較例3及比較例4的陽極剝除伏安法更改為使用原子吸收光譜法（atomic absorption spectroscopy，AAS），以原子吸收光譜儀來檢測鉛離子的濃度，其結果亦記錄於表2。In addition, the concentrations of lead ions measured in Experimental Example 2, Comparative Example 3, and Comparative Example 4 are recorded in Table 2. The anode stripping voltammetry of Experimental Example 2, Comparative Example 3, and Comparative Example 4 was changed to use atomic absorption spectroscopy (AAS) to detect the concentration of lead ions by atomic absorption spectrometry. The results were also Recorded in Table 2.
表2
根據表2，可知實驗例2中，經本發明的吸附、沖洗及脫附處理後再使用陽極剝除伏安法可以測得接近鉛離子的實際濃度。反觀比較例3中的鉛離子濃度則完全無法測出。可知經本發明的重金屬離子的檢測方法，可以改善基質造成的訊號偏移及抑制，並且可以提升定性及定量的檢測結果的準確度。According to Table 2, it can be seen that in Experimental Example 2, the actual concentration close to the lead ions can be measured using the anode stripping voltammetry after the adsorption, washing and desorption treatments of the present invention. In contrast, the lead ion concentration in Comparative Example 3 could not be measured at all. It can be known that the method for detecting heavy metal ions of the present invention can improve signal shift and suppression caused by a matrix, and can improve the accuracy of qualitative and quantitative detection results.
＜實驗例3＞＜ Experimental Example 3 ＞
將銅離子拓印高分子（製造方法同實驗例1）及鉛離子拓印高分子（製造方法同實驗例2）與矽砂（商品名：Aldrich 806765，粒徑為3 μm，購自Sigma Aldrich）均勻混合。然後填充於離子拓印高分子管。接著，提供導電度大約為2,400微西門子/公分的模擬廢水，且添加10 ppm的銅離子及10 ppm的鉛離子至模擬廢水。Copper ion imprinted polymer (manufacturing method is the same as Experimental Example 1), lead ion imprinted polymer (manufacturing method is the same as Experimental Example 2) and silica sand (trade name: Aldrich 806765, particle size 3 μm, purchased from Sigma Aldrich ) Mix evenly. It is then filled in an ion-imprinted polymer tube. Next, a simulated wastewater having a conductivity of about 2,400 micro Siemens / cm was provided, and 10 ppm of copper ions and 10 ppm of lead ions were added to the simulated wastewater.
之後，使模擬廢水流經具有銅離子拓印高分子及鉛離子拓印高分子的離子拓印高分子管，以對銅離子及鉛離子進行吸附。接著，使用去離子水對離子拓印高分子管進行沖洗，去除基質。然後，使用pH值大約為2的鹽酸脫附銅離子及鉛離子。最後，使用網版印刷三極式電極板來進行陽極剝除伏安法檢測，其結果如圖5的曲線4所示。Then, the simulated wastewater is passed through an ion-imprinted polymer tube having a copper ion-imprinted polymer and a lead-ion imprinted polymer to adsorb copper ions and lead ions. Next, the ion-imprinted polymer tube is rinsed with deionized water to remove the matrix. Then, copper ion and lead ion were desorbed using hydrochloric acid having a pH of about 2. Finally, a screen-printed tripolar electrode plate was used for anodic stripping voltammetry detection, and the result is shown in curve 4 in FIG. 5.
＜比較例5＞〈Comparative example 5〉
提供與實驗例3相同的模擬廢水。接著，添加10 ppm的銅離子及10 ppm的鉛離子至模擬廢水。之後，直接使用網版印刷三極式電極板來對廢水進行陽極剝除伏安法檢測，其結果如圖5的曲線5所示。The same simulated wastewater as in Experimental Example 3 was provided. Next, 10 ppm of copper ions and 10 ppm of lead ions were added to the simulated wastewater. After that, the screen printing tripolar electrode plate was directly used to perform anodic stripping voltammetry on the waste water, and the result is shown in curve 5 in FIG. 5.
＜比較例6＞〈Comparative example 6〉
添加10 ppm的銅離子及10 ppm的鉛離子至去離子水。之後，直接使用網版印刷三極式電極板來對該去離子水進行陽極剝除伏安法檢測，其結果如圖5的曲線6所示。Add 10 ppm of copper ions and 10 ppm of lead ions to deionized water. After that, the screen-printed tripolar electrode plate was directly used to perform anodic stripping voltammetry detection on the deionized water, and the result is shown in curve 6 in FIG. 5.
根據圖5，可知相較於比較例6，比較例5的未經吸附、沖洗及脫附處理的模擬廢水的電位及電流訊號偏移很多，其中鉛離子的電流訊號（圖5的左半部）甚至完全被抑制。反觀實驗例3，其檢測結果與比較例6接近，因此說明經由本發明的重金屬離子的檢測方法，廢水中的基質已經被置換為鹽酸，能夠有效解決陽極剝除伏安法容易受基質干擾造成目標金屬離子的定量及定性分析的準確度降低的問題。According to FIG. 5, compared with Comparative Example 6, it can be seen that the potential and current signals of the simulated wastewater without the adsorption, flushing, and desorption treatments of Comparative Example 5 are much shifted. The current signal of lead ions (the left half of FIG. 5) ) Even completely suppressed. In contrast, experimental example 3 has a detection result close to that of comparative example 6. Therefore, it is shown that by using the method for detecting heavy metal ions of the present invention, the matrix in the wastewater has been replaced with hydrochloric acid, which can effectively solve the problem that the anode stripping voltammetry is easily affected by matrix interference The problem of reducing the accuracy of the quantitative and qualitative analysis of the target metal ion.
此外，圖5也顯示出明顯的銅離子與鉛離子的訊號，因此也說明了可以透過本發明的檢測方法能同時對待檢測廢水中的兩種目標金屬離子依序進行吸附、沖洗及脫附處理，然後對兩種目標金屬離子進行定量及定性分析。基於上述，本發明的重金屬離子的檢測方法可以有效減少廢水中基質造成的訊號偏移及抑制的問題，並且可以提升定性及定量的檢測結果的準確度。此外，本發明的檢測方法能有效檢測低濃度的目標金屬離子。In addition, FIG. 5 also shows obvious signals of copper ions and lead ions, so it also illustrates that the detection method of the present invention can simultaneously perform the adsorption, washing and desorption treatment of two target metal ions in the wastewater to be detected , And then quantitative and qualitative analysis of the two target metal ions. Based on the above, the method for detecting heavy metal ions of the present invention can effectively reduce the problem of signal shift and suppression caused by substrates in wastewater, and can improve the accuracy of qualitative and quantitative detection results. In addition, the detection method of the present invention can effectively detect a target metal ion at a low concentration.
另外，本發明的檢測方法不需要電極修飾，廢水中的多種目標金屬離子可以同時在單一個離子拓印高分子管中依序進行吸附、沖洗及脫附處理，然後直接檢測目標金屬離子的濃度，因此可以達到節省檢測步驟與成本的功效。In addition, the detection method of the present invention does not require electrode modification, and multiple target metal ions in wastewater can be sequentially adsorbed, washed, and desorbed in a single ion-imprinted polymer tube at the same time, and then the concentration of the target metal ions is directly detected. Therefore, the effect of saving detection steps and costs can be achieved.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.
S100、S200、S300、S400‧‧‧步驟S100, S200, S300, S400 ‧‧‧ steps
100‧‧‧廢水100‧‧‧ wastewater
102‧‧‧目標金屬離子102‧‧‧ target metal ion
103‧‧‧非目標物103‧‧‧ non-target
104‧‧‧離子拓印高分子管104‧‧‧Ion Overprint Polymer Tube
106‧‧‧離子拓印高分子106‧‧‧Ion Overprint Polymer
106a‧‧‧第一離子拓印高分子106a‧‧‧The first ion-imprinted polymer
106b‧‧‧第二離子拓印高分子106b‧‧‧Second ion-imprinted polymer
108‧‧‧去離子水108‧‧‧ deionized water
110‧‧‧酸液110‧‧‧acid solution
112‧‧‧檢測容器112‧‧‧test container
114‧‧‧網版印刷三極式電極板114‧‧‧Screen printing tripolar electrode plate
116、130‧‧‧工作電極116, 130‧‧‧ working electrode
118、132‧‧‧輔助電極118, 132‧‧‧Auxiliary electrode
120、134‧‧‧參考電極120, 134‧‧‧Reference electrode
122‧‧‧工作電極傳輸部122‧‧‧Working electrode transmission department
124‧‧‧輔助電極傳輸部124‧‧‧Auxiliary electrode transmission section
126‧‧‧參考電極傳輸部126‧‧‧Reference electrode transmission section
128‧‧‧三極式電極棒128‧‧‧Tripolar electrode rod
136‧‧‧玻璃136‧‧‧ Glass
圖1是本發明一實施例的重金屬離子的檢測方法的流程圖。 圖2為本發明一實施例的重金屬離子的檢測方法的操作示意圖。 圖3為本發明一實施例中使用的網版印刷三極式電極板及三極式電極棒的裝置示意圖。 圖4為本發明的實驗例1、比較例1及比較例2的電位-電流圖。 圖5為本發明的實驗例2、比較例3及比較例4的電位-電流圖。FIG. 1 is a flowchart of a method for detecting heavy metal ions according to an embodiment of the present invention. FIG. 2 is an operation schematic diagram of a method for detecting heavy metal ions according to an embodiment of the present invention. 3 is a schematic diagram of a screen printing tripolar electrode plate and a tripolar electrode rod device used in an embodiment of the present invention. FIG. 4 is a potential-current diagram of Experimental Example 1, Comparative Example 1, and Comparative Example 2 of the present invention. 5 is a potential-current diagram of Experimental Example 2, Comparative Example 3, and Comparative Example 4 of the present invention.
Claims (10)
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| CN105181779A (en) * | 2015-09-18 | 2015-12-23 | 哈尔滨工业大学 | Device and method for online monitoring heavy metal ions in water |
| TWI592651B (en) * | 2016-08-31 | 2017-07-21 | 國立清華大學 | Metal ion detection equipment and metal ion detection method |
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| CN102607999A (en) * | 2011-01-19 | 2012-07-25 | 索尼公司 | Method and device for detecting heavy metal ion in water |
| CN105181779A (en) * | 2015-09-18 | 2015-12-23 | 哈尔滨工业大学 | Device and method for online monitoring heavy metal ions in water |
| TWI592651B (en) * | 2016-08-31 | 2017-07-21 | 國立清華大學 | Metal ion detection equipment and metal ion detection method |
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