KR102068610B1 - Preparation method for detecting arsenic ion and detection method of arsenic ion using the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a sensor for detecting arsenic ions consisting of an electrode coated with an electrically conductive polymer-gold nanoflower composite, and a method for detecting arsenic ions using the same, wherein the nano-material includes the gold and poly terthiophene A sensor for detecting arsenic (As) ions using an electrode surface-modified with a coating layer of a flower composite can selectively detect As (V) or As (III) ions without interfering effects of other active species, in particular As (V) In case of detection, no additional electrodeposition time is required, and when As (III) is detected, a short electrodeposition time of 90 seconds enables stable and rapid detection of trace amounts of As ions present in industrial or ground water to low concentrations. This can be very useful.

Description

Preparation method of sensor for detecting arsenic ion and method for detecting arsenic ion using same {Preparation method for detecting arsenic ion and detection method of arsenic ion using the same}

The present invention relates to a method for manufacturing a sensor for detecting arsenic ions consisting of an electrode coated with an electrically conductive polymer-gold nanoflower composite, and a method for detecting arsenic ions using the same.

Arsenic (As) is one of the most carcinogenic toxic elements present in the earth's crust and groundwater. As contamination of groundwater and drinking water poses a serious threat to human health, and active research is being conducted to address these problems in many environmental fields ( Anal. Chem . 2013, 85, 2673 ).

Chronic toxicity of arsenic in drinking water is known to cause various types of cancer and sclerosis ( Environ. Sci . Technol . 2004, 38, 924 ), while arsenic is As (V), As (III), As (0). ) And As (-III). The trivalent oxidation state of arsenic is not stable and can be oxidized to pentavalent arsenic ( Environ. Sci . Technol . 2002, 36, 2213; Anal. Chem . 2004, 76, 7137 ). To date, many methods for the preservation of arsenic species and various field detection techniques for the determination of As (V) and As (III) species have been developed.

Representative known arsenic ion detection methods include high-performance liquid chromatography-inductive coupling plasma mass spectrometry (HPLCICPMS) and HPLC atomic fluorescence spectrometry (HPLCAFS). . These methods have high accuracy and resolution, but there are disadvantages such as long time pretreatment and detection time and high cost in one detection. The World Health Organization (WHO) recommends lowering the maximum contaminant concentration of arsenic in drinking water to 2-10 ppb, which requires high sensitivity sensors and efficient and inexpensive methods for detecting trace As ions in drinking water.

Electrochemical methods are cost-effective and rapid in comparison to laboratory-based instruments such as inductively coupled plasma spectroscopy (ICPMS), atomic absorption spectroscopy (ABS) and ion chromatography. It is the most promising technology available in the field.

Among electrochemical methods, Square Wave Voltammetry (SWV) and Square Wave Anodic Stripping Voltammetry (SWASV) analysis can detect trace elements under excellent oxidation sensitivity and unique oxidation state. , the analysis process can minutes depositing arsenic ions to the electrode for electrochemically ^{(as 3 + + 3e - →} as 0) , and then re-oxidizing the metal by the above reverse scan (as ⁰ Analyzed via a) step ^- → As ^{3 + +} 3e. Signal-to-noise enhancement with reduction in capacitance background with the introduction of pulsed-voltage current technology can provide significantly better detection limits than expensive spectroscopic techniques, but it is possible to use platinum (Pt), gold ( Electrodes made of metal materials such as Au) and silver (Ag) have a problem of causing toxicity.

Republic of Korea Patent Publication No. 10-2017-0002787 (published Jan. 9, 2017)

The present invention is coated with an electrically conductive polymer-gold nanoflower complex to selectively analyze and quantitatively detect arsenic trivalent (As (III)) or arsenic pentavalent (As (V)) without interfering with other active species. The present invention provides a method for manufacturing a sensor for detecting arsenic ion using the prepared electrode and a method for detecting arsenic ion using the same.

The present invention is an electrode; It is formed on the electrode, and provides a sensor for detecting arsenic (As) ion, characterized in that consisting of a coating layer of nano-flower composite including gold (Au) and poly terthiophene.

The present invention comprises the steps of preparing a mixed solution containing a gold precursor, a nickel precursor and a terthiophene monomer (first step); Immersing the electrode in the mixed solution and applying a voltage to form a coating layer made of gold, nickel and polythiophene on the electrode (second step); And it provides a method for manufacturing a sensor for arsenic (As) ion detection comprising the step of removing nickel (third step) using a cyclic voltammetry method on the electrode formed with the coating layer.

In addition, the present invention comprises the steps of adjusting the pH of the sample solution to 1 to 2; And inserting the sample solution and the electrolyte into the arsenic (As) ion detection sensor and applying an electric potential to the arsenic (As) ion detection method.

According to the present invention, a sensor for detecting arsenic (As) ions using an electrode surface-modified with a coating layer of a nano-flower composite including gold (Au) and poly terthiophene may be used as As (V) or without interfering with other active species. As (III) ions can be selectively detected, especially for As (V) detection, no additional electrodeposition time is required, and for As (III) detection, a short electrodeposition time of 90 seconds is present in industrial or ground water. As a small amount of As ions can be detected stably and quickly to low concentrations, it can be very useful for field analysis.

1 shows a representative schematic diagram of a sensor for detecting As (V) ions according to an embodiment of the present invention.
Figure 2 is a result of confirming the current value for the electrically conductive polymers of the composite plating layer of the nanoscale flower structure (nanoflower, NF) according to Example 1, Figure 2 (A) is an NFAu-TCA electrode, Figure 2 ( B) is an NFAu-TBA electrode, FIG. 2 (C) is an NFAu-APT electrode, FIG. 2 (D) is an NFAu-2,3-DAN electrode, and FIG. 2 (E) is an NFAu-1,8-DAN electrode. This is the result of detecting 500ppb As (V) with a pentavalent arsenic ion detection sensor and comparing the sensitivity.
3 is a result of confirming the surface image of the electrode of the modified composite plating layer of the nano-size flower structure according to Example 1, Figure 3 (A) and (b) is a SEM image of the surface of the NFAu-TCA electrode (C) is an EDS image after dealloyed of the NFAu-TCA electrode surface, and (d), (e), (f), (g) and (h) are AuNi after dealloyed of the NFAu-TCA electrode surface, respectively. A diagram showing EDS mapping results for, Au, Ni, O, and S elements. FIG. 3 (B) shows the EDS spectra and atomic ratio (At%) for each element before dealloyed (a) and (b) after the NFAu-TCA electrode surface, and FIG. 3 (C) shows the NFAu-TCA electrode. (A) survey, (b) S2p, (c) Au4f and (d) Ni2p XPS spectra of the electrode surface before and after dealloyed on the surface.
4 is a result of checking the optimization conditions for As (V) of 100 ppb for the electrode modified nano-flower composite plating layer according to Example 1, Figure 4 (A) is a concentration of Ni, Figure 4 (B) Is the concentration of the monomer, Figure 4 (C) is the electrodeposition time of gold, Figure 4 (D) is the result of checking the optimization conditions for the type of electrolyte and the effect of pH and Figure 4 (E).
5 is a result of confirming the arsenic ion detection limit using the electrode modified nano-flower composite plating layer according to Example 1, Figure 5 (A) is for detecting As (V) ion (a) at 1 ppb It is a result showing the signal change for each concentration obtained by using the square wave voltammetry (SWV) in the concentration range of 400 ppb, (b) is a diagram showing a calibration curve for the detection corresponding thereto, Figure 5 (B ) Shows the change of signal by concentration obtained by using Square Wave Anodic Stripping Voltammetry (SWASV) in concentration range of 1 ppb to 3 ppm to detect As (III) ion. , (b) shows the corresponding calibration curve for detection.
6 is a result of confirming the interference effect in the detection of arsenic ion using the electrode modified nano-flower composite plating layer according to Example 1, Figure 6 (A) is to confirm the interference effect on As (V) ions (a) shows signal changes for other heavy metal ions (100.0 ppb Cr (VI), Se (IV), Fe (III), V (V), Co (II)) obtained using square wave voltammetry; (b) is a result plot for the corresponding interference action, and (a) of (B) is a signal for other heavy metal ions obtained using square wave stripping voltammetry (SWASV) for As (III) ions. And (b) is a result analysis for the corresponding interference action.
FIG. 7 illustrates As (V) contained in an actual wastewater sample by square wave voltammetry (SWV) to confirm applicability to an actual sample using the electrode modified with the nanoflower composite plating layer according to Example 1. FIG. The detection result was classified into upper, middle and lower according to the handling point of the wastewater sample, and each sample was classified into a supernatant or a mixed sample, and the concentration was quantified by a standard addition method.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention, while research and development on the manufacturing method of the sensor for detecting heavy metals, different As (V) or As (III) by using a sensor comprising a nano-plated composite layer of gold and poly terthiophene The present invention has been completed by discovering that selective detection in the field can be performed immediately in a short time without the interference effect of the active species.

The present invention is an electrode; The sensor for arsenic (As) ion detection, which is formed on the electrode and comprises a coating layer of a nanoflower composite including gold (Au) and poly terthiophene, may be provided.

The nano flower composite may be one having an average diameter of 250 to 500 nm.

The arsenic (As) ions may be selected from the group consisting of As (III) and As (V).

The present invention comprises the steps of preparing a mixed solution containing a gold precursor, a nickel precursor and a terthiophene monomer (first step); Immersing the electrode in the mixed solution and applying a voltage to form a coating layer made of gold, nickel and polythiophene on the electrode (second step); And removing nickel using a cyclic voltammetry method on the electrode on which the coating layer is formed (third step).

The gold precursor may be any one selected from the group consisting of gold chloride · trihydrate (HAuCl ₄ · 3H ₂ O), gold chloride (AuCl), and potassium potassium chloride (KAuCl ₄ ).

The nickel precursor may be any one selected from the group consisting of nickel sulfide hexahydrate (NiSO ₄ .6H ₂ O), nickel chloride (II) (NiCl ₂ ), and nickel chloride hexahydrate (NiCl ₂ .6H ₂ O). Can be.

The terthiophene monomer is 5,2 ': 5', 2 "-terthiophene-3'-carboxylic acid (5,2 ': 5', 2" -Terthiophene-3'-carboxylic acid; hereinafter 'TCA') , (2,2 ': 5', 2 "-terthiophene-3'-p-benzoic acid (2,2 ': 5', 2" -terthiophene-3'-p-benzoic acid; hereinafter 'TBA') ), (3-([2,2 ': 5', 2 "-terthiophene] -3'-yl) -5-aminobenzoic acid (3-([2,2 ': 5', 2" -terthiophen ] -3'-yl) -5-aminobenzoic acid (hereinafter 'TTABA')), (3 '-(pyrimidyl2-amino) -2,2': 5 ', 2 "-terthiophene (3'- (pyrimidyl-2-amino) -2,2 ': 5', 2 "-terthiophene (hereinafter 'PATT')), and ((2,2 ': 5', 2" -terthiophene) -3 ', 4'-diamine (([2,2 ': 5', 2 ''-terthiophene] -3 ', 4'-diamine); hereafter' DATT ') may be any one selected from the group consisting of.

The second step may be to form a coating layer on the electrode by immersing the electrode in the mixed solution prepared in the first step and applying a current of -1 to -3V for 800 to 900 seconds.

The third step may be to remove the nickel by scanning at a rate of 150 to 250 kHz / s at 0 to +1.5 V using cyclic voltammetry to the electrode on the coating layer.

In addition, the present invention comprises the steps of adjusting the pH of the sample solution to 1 to 2; And inserting the sample solution and the electrolyte into the arsenic (As) ion detection sensor according to the manufacturing method and applying a potential to the arsenic (As) ion detection method.

The arsenic (As) ion detection method may be to detect As (V) ions by applying a reduction potential in the range of +0.2 to -0.4 V.

The arsenic (As) ion detection method may be to detect As (III) ions by applying an oxidation potential in the range of -0.2 to +0.65 V.

The electrolyte may be a arsenic (As) ion detection method, characterized in that the nitric acid solution.

Hereinafter, examples will be described in detail to help understand the present invention. However, the following examples are merely to illustrate the content of the present invention is not limited to the scope of the present invention. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

< Reference Example > Substance

Nickel sulfide hexahydrate (NiSO ₄ · 6H ₂ O) (≥99.99% trace metals basis) was purchased from Sigma-Aldrich, USA. Other chemicals were obtained from the American Chemical Society (ACS). Purified to reagent grades. Distilled water (18 MΩ / cm) was also obtained in a Millipore system.

< Example  1> Manufacture of heavy metal sensor

One. Thesiophene  Monomer ( TCA ) synthesis

5,2 ': 5', 2 "-terthiophene-3'-carboxylic acid (5,2 ': 5', 2" -Terthiophene-3'-carboxylic acid (TCA)) has been previously known (Synthetic. Met. , 2002, 126, 105-110).

2. Fabrication of As (V) or As (III) ion detection sensor

A sensor for detecting As (III) or As (V) ions was manufactured by the same process as in FIG. 1.

In order to modify the surface of the glassy carbon electrode ('GCE'), nickel sulfide hexahydrate (NiSO ₄ · 6H ₂ O, 1.5 ×) in a gold plating solution (24k) (Young Jin Jewelry Tool Co. Ltd.) was used. A mixed solution was prepared by dissolving 10.0 μl of dimethyl sulfoxide (DMSO) in which 10 ⁻² M) and TCA (1.0 × 10 ⁻² M) were dissolved.

After dipping the glassy carbon electrode (GCE) in the prepared mixed solution, a constant voltage of -1.0 V was flowed for 900 seconds to form a composite plating layer of gold, nickel, and poly TCA on the glassy carbon electrode (GCE) surface. .

The glassy carbon electrode (GCE) in which the composite plating layer of gold, nickel, and poly TCA was modified was subjected to cyclic voltammetry (hereinafter, 'CV') in a sulfuric acid solution (1.5 M) from 0V to + 1.5V. Nickel was selectively removed by scanning at a rate of 200 mA / s to fabricate an electrode having a composite plating layer composed of nanoflower gold-poly TCA.

< Experimental Example  1> Sensor performance evaluation

1. Sample Solution Preparation

Samples for detection of As (III) were prepared in a standard solution containing 1000 ppm of As (III) ions. For As (V) detection, the sample was prepared in a standard solution containing 1000 ppm of As (III) ions. As (V) was used with ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) (≥98%, ACS reagent, Sigma-Aldrich, USA).

It was prepared by diluting As ions by concentration using a solution prepared as described above as a stock solution. Electrode with modified composite plating layer consisting of nano flower gold-poly TCA was transferred to conduit containing only supporting electrolyte solution, and then voltammetric analysis was performed. SWV and SWSV analysis at low concentration were performed in the same preliminary concentration solution containing electrolyte. Was performed.

2. Cyclic voltammetry ( CV ), Square wave Voltammetric ( SWV ) And Square wave  excoriation Voltammetric (SWSV) Analysis Method

The cyclic voltammetry (CV), square wave voltammetry (SWV) and square wave stripping voltammetry (SWSV) analyzes are known as potentiostat / galvanostat. , Kosentech Model KST-P2, Korea).

The composite plated layer made of the nano flower gold-poly TCA fabricated in Example 1 was modified with a glassy carbon electrode (GCE) (diameter: 3.0 mm), Ag / AgCl, and platinum wires as working electrodes, auxiliary electrodes, and counter electrodes, respectively. The used 3-electrode system was used.

SWV analysis was measured by scanning a reduction potential of -0.4 V at +0.2 V compared to Ag / AgCl. SWSV analysis was measured by scanning the oxidation potential of -0.2 to +0.65 V compared to Ag / AgCl with a scan rate of 50 mV / s.

3. Characterization of electrode

First, the electrode was modified step by step and the characteristics of each modified electrode were confirmed using SWV.

As a result, NFAu-TBA electrode (B), NFAu because the peak current of the electrode (A) modified with a composite plating layer consisting of nano-flower gold-poly TCA (NFAu-TCA) as shown in Figure 2 was larger than other electrodes Compared with the APT electrode (C), the NFAu-2, 3-DAN electrode (D), and the NFAu-1, 8-DAN electrode (E), it was confirmed that it was suitable for detection of As (V).

In addition, referring to Figure 3 (A), it can be confirmed that the surface of the electrode modified with a composite plating layer consisting of nanoflower gold-poly TCA was a nanoflower structure, the average diameter of the nanoflower structure was about 250-500 nm .

From the results, it was confirmed that in the composite plating layer made of gold, nickel and poly TCA, nickel was selectively removed to successfully form a composite plating layer made of nano-sized nano flower gold-poly TCA on the surface of the glassy carbon electrode (GCE). Could.

Figure 3 (B) is before and after dealloying of the surface of the NFG-TCA electrode, (c) EDS image, (d) AuNi, (e) Au, (f) Ni, (g) O, (h ) Shows EDS results for S element, Ni was 5.84% (at%) before dealloying, but Ni was removed as 0.34% after dealloying, and C, O, Ni, Au and S elements The atomic ratio of was found to be 54.34, 8.04, 0.34, 30.21 and 7.07%, respectively.

FIG. 3 (C) shows the results of the survey, (b) S2p, (c) Au4f, and (d) Ni2p XPS spectra before and after dealloying of the nanoflower gold-poly TCA electrode surface. S2p peak was confirmed that the polyether thiophene in the vicinity of (b), (c) have been identified, each Au4f _7/2 and Au4f _5/2 peak at about 83.8 and 87.4 eV is. (c) have been identified, each Ni2p _5/2 peak at Ni2p _3/2 near the 870.1 eV in the vicinity of 853.1 eV and 858.6.4 are.

(c) to (d), (i) is a gold plating layer, (ii) is a gold-nickel plating layer, (iii) is a gold-nickel-TCA plating layer, and (iV) is a composite plating layer consisting of nanoflower gold-poly TCA. with, (c) the strength (intensity) variation of the _{5/2 7/2} Au4f peak and Au4f each plating layer is not large, the nano gold flower selectively removing the Ni in (iV) of (d) - poly TCA composite plating layer It was confirmed that the strength of silver Ni was significantly reduced.

4. Identification of optimization conditions of detection parameters

In order to optimize the detection environment of the sensor, (D) Ni concentration of the nanoflower gold-poly TCA composite plating layer, (B) TCA concentration, (C) gold electrodeposition time, and (D) The change of current according to the type of pH and (E) electrolyte was observed.

As a result, the current increased as the concentration of Ni increased from 0 to 50mM as shown in FIG. 4 (A), and the peak current decreased when the concentration of Ni exceeded 50mM. Referring to FIG. 4 (B), the concentration of TCA was increased. The peak current increased with increasing from 1 μM to 10 μM, and above 10 μM the peak current decreased. As the electrodeposition time of gold increased from 400 seconds to 900 seconds as shown in FIG. 4 (C), the current increased, and the peak current decreased after 900 seconds.

In addition, referring to FIG. 4 (D), the current increased as the pH of the solution increased from 0.5 to 1.5, and the peak current decreased when the pH was above 1.5, in consideration of detection sensitivity and detection ability. In the experiment for optimizing detection parameters, the pH of the sample solution was set to 1.5.

The detection of As (V) was carried out while varying the supporting electrolyte to 0.1 M of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or perchloric acid, respectively to confirm the optimum electrolyte.

As a result, when using nitric acid as a supporting electrolyte as shown in Figure 4 (E), the peak current is larger than when using other electrolytes, the electrolyte to be used in subsequent experiments was determined to be a nitric acid solution.

5. Interference effect

When detecting As (III) or As (V) ions with an electrode modified with a composite plating layer composed of nano flower gold-poly TCA, Cr (VI) and Se (III), Fe (III), V The interfering effects of (V) and Co (II) were analyzed. At this time, the concentration of the metal ions to see the interference effect was fixed to 100 ppb.

As a result, referring to FIG. 6 (B), no additional peak was observed in As (III), and the peak current also showed a difference of about 10.0% within an error range.

In the case of As (V) of FIG. 6 (A), no additional peak was observed, and the peak current also showed a difference of about 5.9% within an error range.

As the ion detection sensor including the electrode modified with a composite plating layer consisting of nano flower gold-poly TCA from the above results can detect a small amount of As (III) or As (V) without interference of other active species This was confirmed.

6. Identify calibration curve and detection limits

As the optimal experimental conditions confirmed in the previous experiment, the calibration curve for detecting As (III) or As (V) was obtained.

 In the case of As (V), the detection experiment was performed using SWV with increasing concentration from 1 ppb to 400 ppb as shown in (a) of FIG. 5 (A), and the peak current shown in FIG. As shown in b), the calibration curve was 0.99, and the dynamic range of the calibration curve was 1 ppb to 300 ppb and 300 ppb to 400 ppb.

As a result, the detection limit calculated using the slope of the calibration curve was found to be 0.15 ppb.

In the case of As (III), detection experiments were performed using SWSV while increasing the concentration from 1 ppb to 3 ppm as shown in FIG. 5 (B). The peak current at this time is represented by (b) calibration curve of FIG. 4 (B), the correlation coefficient of the calibration curve was 0.97, and the dynamic range of the calibration curve was 1 ppb to 1 ppm and 1 ppm to 3 ppm.

As a result, the detection limit calculated using the slope of the calibration curve was found to be 0.74 ppb.

From the above results, it was determined that the As (III) or As (V) ion detection sensor including the electrode modified with a composite plating layer made of nanoflower gold-poly TCA could measure As ions even in actual samples, that is, tap water. .

7. Real Sample Analysis

In order to confirm the applicability of the sensor including the electrode modified with a composite plating layer composed of nano flower gold-poly TCA, the As (V) contained in the wastewater was detected using the SWV method.

Referring to FIG. 7, the samples were separated into upper, middle, and lower portions according to the handling positions of the wastewater, and these samples were respectively classified into supernatants or mixed samples, and then concentrations were quantified using a standard addition method. The supernatant (20 times diluted), upper mix (40 times), middle supernatant (80 times), middle mix (80 times), lower supernatant (90 times) and lower mix (80 times) of each sample were calibrated to pH 1.5. The concentrations were quantified by adding 5.0, 10.0, 15.0, 20.0 and 300.0 ppb to standard heavy metal ions.

As a result, As (V) ions were detected in each sample as shown in Table 1, and similar As (V) ion concentrations were shown in the results of comparative analysis with the ICP-MS results. The error in As (V) concentration is due to the concentration change with sample analysis time.

From the above results, it was confirmed that the sensor including the electrode modified with the composite plating layer made of nanoflower gold-poly TCA can be applied as a sensor capable of effectively detecting As (V) ions contained in the actual wastewater.

Having described the specific part of the present invention in detail, it is apparent to those of ordinary skill in the art that such a specific description is merely a preferred embodiment, thereby not limiting the scope of the present invention. something to do. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (13)

electrode;
Gold (Au) and poly 5,2 ': 5', 2 "-terthiophene-3'-carboxylic acid (5,2 ': 5', 2"-Terthiophene-3'-carboxylic acid) formed on the electrode A sensor comprising a coating layer of a nanoflower composite comprising acid;
The sensor for detecting arsenic (As) ions, characterized in that for detecting As (III) and As (V) ions. The sensor for detecting arsenic (As) ions according to claim 1, wherein the nanoflower composite has an average diameter of 250 to 500 nm. delete Preparing a mixed solution containing a gold precursor, a nickel precursor, and 5,2 ': 5', 2 "-terthiophene-3'-carboxylic acid (TCA) (first step);
Immersing the electrode in the mixed solution and applying a current of -1 to -3V for 800 to 900 seconds to form a nanoflower composite coating layer made of gold, nickel and poly TCA on the electrode (second step); And
Method of manufacturing a sensor for arsenic (As) ion detection comprising the step of removing nickel (third step) using the cyclic voltammetry method on the electrode formed with the coating layer. The arsenic (As) of claim 4, wherein the gold precursor is any one selected from the group consisting of gold chloride trihydrate (HAuCl ₄ · 3H ₂ O), gold chloride (AuCl), and gold potassium chloride (KAuCl ₄ ). Ion detection sensor manufacturing method. The method of claim 4, wherein the nickel precursor is a group consisting of nickel sulfide hexahydrate (NiSO ₄ · 6H ₂ O), nickel chloride (II) (NiCl ₂ ), and nickel chloride hexahydrate (NiCl ₂ · 6H ₂ O). Arsenic (As) ion detection sensor manufacturing method, characterized in that any one selected from. delete delete The method of claim 4, wherein the third step is to remove the nickel by scanning at a rate of 150 to 250 ㎃ / s at 0 to +1.5 V using cyclic voltammetry to the electrode on the coating layer is formed. Arsenic (As) ion detection sensor manufacturing method. Adjusting the pH of the sample solution to 1-2; And
Arsenic (As) ion detection method comprising the step of applying the potential to the sample solution and the electrolyte in the arsenic (As) ion detection sensor of claim 1. The arsenic (As) ion detection method of claim 10, wherein the arsenic (As) ion detection method detects As (V) ions by applying a reduction potential in the range of +0.2 to -0.4 V. 12. The method of claim 10, wherein the arsenic (As) ion detection method detects As (III) ions by applying an oxidation potential in the range of -0.2 to +0.65 V. The arsenic (As) ion detection method according to claim 10, wherein the electrolyte is a nitric acid solution.

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