KR20150012072A - Hydrogen peroxide detection sensor and method for fabricating the working electrode of the same - Google Patents

Abstract

The present invention relates to a hydrogen peroxide measuring sensor and a working electrode manufacture method thereof. Provided is the hydrogen peroxide measuring sensor measuring highly concentrated hydrogen peroxide included in industrial waste water without enzymes. The hydrogen peroxide measuring sensor comprises: a reference electrode; a counter electrode; and a working electrode including a copper oxide nanoflower electrode. The copper oxide nanoflower electrode includes a copper oxide electrode and a polyimide tape layer formed on one side of the copper oxide electrode.

Description

TECHNICAL FIELD [0001] The present invention relates to a hydrogen peroxide measurement sensor and a method for manufacturing a working electrode of a hydrogen peroxide measurement sensor.

The present invention relates to a hydrogen peroxide measurement sensor and a method of manufacturing a working electrode of a hydrogen peroxide measurement sensor.

Techniques for quantifying hydrogen peroxide include titration with permanganic acid, spectroscopy, and electrochemical methods. Among these, electrochemical methods have advantages such as high sensitivity, fast response time, and wide dynamic range.

In addition, in the measurement of hydrogen peroxide concentration, enzyme-based sensors are being studied in combination with electrochemical methods. However, in the case of an enzyme-based sensor, there is a problem of stability, and a hydrogen peroxide sensor based on a copper oxide nanoflower electrode having characteristics of high stability and large surface area without using an enzyme is being studied.

A problem to be solved by the present invention is to provide a hydrogen peroxide measurement sensor capable of measuring hydrogen peroxide at a high concentration contained in industrial wastewater without enzymes.

Another problem to be solved by the present invention is to provide a method of manufacturing a working electrode of a hydrogen peroxide measuring sensor capable of measuring a high concentration of hydrogen peroxide contained in industrial wastewater without enzymes.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to another aspect of the present invention, there is provided a hydrogen peroxide sensor comprising a reference electrode, a counter electrode, and a working electrode including a copper oxide nanoflow electrode, wherein the copper oxide nanoflow electrode comprises a copper oxide electrode, And a polyimide tape layer formed on one surface of the electrode.

And a measuring unit for measuring a concentration of hydrogen peroxide contained in the solution through the working electrode. The current value for each concentration of hydrogen peroxide contained in the solution is stored in the measuring unit, and the concentration of hydrogen peroxide may be 100 to 1000 ppm.

The measured current value may be proportional to the hydrogen peroxide concentration.

The solution may contain an enzyme.

The reference electrode may include an Ag / Agcl electrode.

The potential of the working electrode is adjusted based on the potential of the reference electrode, the current flows between the working electrode and the counter electrode, and the counter electrode may include a platinum electrode.

Another embodiment of the hydrogen peroxide measurement sensor of the present invention for solving the above problems is a method for measuring a hydrogen peroxide solution, comprising: a reference electrode including an Ag / Agcl electrode; a counter electrode including a platinum electrode; a working electrode including a copper oxide nanoflow electrode; Wherein the concentration of hydrogen peroxide in the solution is in the range of 100 to 1000 ppm, and the copper oxide nanoflow electrode is a copper oxide And a polyimide tape layer formed on the electrode and the copper oxide electrode.

용액을 반응시키는 반응 공정을 수행하고, 반응 공정을 수행한 후 냉각 공정을 수행하고, 냉각 공정 후 세척 공정을 통해 산화구리 나노플라워 전극을 형성하는 것을 포함한다.According to another aspect of the present invention, there is provided a method of manufacturing a working electrode for a hydrogen peroxide sensor, comprising: a) providing a copper electrode and a NaOH solution in a PFA (Perfluoroalkoxy)

And then performing a cooling process after performing a reaction process, and forming a copper oxide nanoflow electrode through a cleaning process after the cooling process.

During the reaction process, the temperature of the PFA vessel can be maintained at 41 to 42 ° C.

And forming a polyimide tape layer on one side of the copper electrode.

Other specific details of the invention are included in the detailed description and drawings.

1 is a conceptual diagram of a hydrogen peroxide measurement sensor according to an embodiment of the present invention.
2 is a circuit diagram of a hydrogen peroxide measurement sensor according to an embodiment of the present invention.
3 is a block diagram illustrating the measuring unit of Fig.
4 to 11 are views illustrating a method of manufacturing a working electrode of a hydrogen peroxide measurement sensor according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Although the first, second, etc. are used to describe various elements, components and / or sections, it is needless to say that these elements, components and / or sections are not limited by these terms. These terms are only used to distinguish one element, element or section from another element, element or section. Therefore, it goes without saying that the first element, the first element or the first section mentioned below may be the second element, the second element or the second section within the technical spirit of the present invention.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. It is noted that the terms "comprises" and / or "comprising" used in the specification are intended to be inclusive in a manner similar to the inclusion of a stated element, step, operation and / Or formation is not excluded.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. And commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

Hereinafter, a hydrogen peroxide sensor according to an embodiment of the present invention will be described with reference to FIGS. 1 to 3. FIG.

1 is a conceptual diagram of a hydrogen peroxide measurement sensor according to an embodiment of the present invention. 2 is a circuit diagram of a hydrogen peroxide measurement sensor according to an embodiment of the present invention. 3 is a block diagram illustrating the measuring unit of Fig.

1 and 2, the hydrogen peroxide measurement sensor 1 includes a reference electrode 100, a working electrode 110, a counter electrode 120, and a measurement unit 200. The hydrogen peroxide measurement sensor 1 may be implemented as a three-electrode system including a reference electrode 100, a working electrode 110, and a counter electrode 120.

The reference electrode 100 may comprise, for example, an Ag / Agcl electrode. Ag / Agcl electrodes can be formed by depositing Agcl on Ag.

The working electrode 110 is an electrode used for causing a desired reaction and is also an electrode to be measured. In addition, the working electrode 110 according to an embodiment of the present invention may include, for example, a copper oxide nanoflow electrode.

The working electrode 110 using a copper oxide nanoflower as an electrode has a high chemical stability and a large surface area, and can exhibit electrocatalytic action. Therefore, by using the copper oxide nanoflower electrode as the working electrode 110, it is possible to realize the hydrogen oxide measuring sensor 1 in a high concentration range without using the enzyme.

The working electrode 110 may include a copper oxide electrode and a polyimide tape layer formed on one surface of the copper oxide electrode. Specifically, when the working electrode 110 is grown from the copper electrode, a polyimide tape layer may be formed on one side of the copper electrode to prevent the front and back sides of the working electrode 110 from being formed differently.

The polyimide tape layer may be formed by attaching a polyimide tape to one surface of a copper electrode. By forming the polyimide tape layer, it is possible to prevent the working electrode 110 from being formed unevenly.

The counter electrode 120 may comprise, for example, a platinum electrode. Also, the counter electrode 120 may function as an electrochemical circuit in the three-electrode system.

Referring to FIG. 3, the measuring unit 200 may include a potentiostat apparatus 205 and a storage apparatus 207.

Specifically, the potentiostat apparatus 205 can perform the electrochemical measurement using the working electrode 110. Electrochemical measurements can be said to analyze the chemical response of a system to a given stimulus when an electrical stimulus is applied to a given system. In other words, it can be said to measure the movement (oxidation or reduction) of electrons accompanied by a substance in relation to electric stimulation. These oxidation and reduction reactions are referred to as redox reactions. Studies on these reactions are based on not only concentration of active species, equilibrium constant, reaction mechanism, but also a lot of information about a series of phenomena such as electron transfer reaction and adsorption on the electrode surface . Since the response type of a given system in each experiment depends on which variable is used as a stimulus signal, a lot of information can be obtained by representing the obtained response type in various forms using various variables. The electrochemical measurement can be classified according to the control variables and the signals to be observed, for example, the linear main prior method, the cyclic voltammetric method, the time zone current method, the time zone charge method, the time zone potential difference method, the polarography method and the impedance method . In an embodiment of the present invention, the cyclic voltammetric method will be described as an example, but the present invention is not limited thereto.

The storage device 207 may store a current value for each concentration of hydrogen peroxide. The concentration range of hydrogen peroxide according to an embodiment of the present invention may include 100 to 1000 ppm, but is not limited thereto. The current value by concentration of hydrogen peroxide stored in the storage device 207 may include, for example, a reduction current value by concentration of hydrogen peroxide.

Referring again to FIGS. 2 and 3, the potential of the working electrode 110 of the hydrogen peroxide measurement sensor 1 according to an embodiment of the present invention can be adjusted based on the reference electrode 100. That is, the potential between the reference electrode 100 and the working electrode 110 can be adjusted by the potential adjuster VA. At this time, the potential difference between the working electrode 110 and the reference electrode 100 can be accurately measured regardless of the current value flowing by the electrode reaction.

In addition, unlike the two-electrode system, the current i flows into the counter electrode 120 rather than the reference electrode 100, thereby preventing a voltage drop due to polarization of the reference electrode 100 or resistance of the solution.

The potentiostat apparatus 205 can measure the current value in the solution through the working electrode 110. Here, since the electrocatalytic copper oxide nanoflow electrode is used as the working electrode 110, the solution may contain no enzyme. The current value may also include, for example, a reduction current value.

The current value measured through the potentiostat apparatus 205 is compared with the current value of the hydrogen peroxide concentration stored in the storage device 207, and the concentration of the corresponding hydrogen peroxide can be derived through the comparison process.

The hydrogen peroxide measurement sensor 1 according to an embodiment of the present invention uses a copper oxide electrode in the form of a nanoflower having a wide surface area and excellent chemical stability as the working electrode 110 to measure the concentration of hydrogen peroxide 100 To 1000 ppm) can be measured without enzyme. Also, the current value measured by the hydrogen peroxide measurement sensor 1 can increase linearly in proportion to the concentration of hydrogen peroxide (concentration range of 100 to 1000 ppm), and an experimental example thereof will be described later.

4 to 11 are views illustrating a method of manufacturing a working electrode of a hydrogen peroxide measurement sensor according to an embodiment of the present invention.

4 is a flowchart of a method of manufacturing a working electrode of a hydrogen peroxide measurement sensor according to an embodiment of the present invention. 5 is a view for explaining S300 of FIG. 6 and 7 are views for explaining a change in position of the PFA (perfluoroalkoxy) container in FIG. FIGS. 8 to 10 are diagrams showing copper oxide nanoflowers according to the reaction time at S300 in FIG. 11 is a graph showing a current value of hydrogen peroxide concentration measured using the copper oxide nanoflower electrode of FIG.

용액과 반응시킨다(S300). 예를 들어, 열수 조건(hydrothermal condition) 하에 별도의 압력 인가 장치를 사용하지 않은 상태에서 NaOH 용액 및

용액과 반응시킬 수 있다. 구체적으로, 10M 농도의 NaOH 용액과 1M 농도의

용액, 그리고 정제수(DI water)가 S300의 반응을 위해 사용될 수 있다. (이하부터, 10M 농도의 NaOH 용액과 1M 농도의

용액, 그리고 정제수(DI water)의 혼합 용액을 반응 용액이라 하겠다.) 4 and 5, first, the copper electrode 230 is immersed in an NaOH solution and /

(S300). For example, under a hydrothermal condition, a solution of NaOH and < RTI ID = 0.0 >

Lt; / RTI > solution. Specifically, a 10M NaOH solution and a 1M concentration

Solution, and DI water may be used for the reaction of S300. (Hereinafter, referred to as a 10M concentration NaOH solution and a 1M concentration

Solution, and purified water (DI water) is called the reaction solution.)

The copper electrode 230 may comprise, for example, a copper foil piece having a very high purity. In addition, when the copper electrode 230 is reacted with the reaction solution, a polyimide tape layer is formed only on one side of the copper electrode 230, so that only the other side of the copper electrode can react with the reaction solution. That is, it is possible to prevent the front surface and the back surface from being formed differently when the copper oxide nanoflow electrode is formed.

용액을 추가할 수 있다. When the above reaction solution is prepared, the copper electrode 230 is put into a mixed solution of purified water and NaOH,

Solution can be added.

The reaction vessel 220 may include, for example, a PFA (Perfluoroalkoxy) vessel.

The PFA (Perfluoroalkoxy) vessel 220 may include a cup 220a and a cap 220b, and the PFA vessel may be capable of heating at -200 ° C to 260 ° C. The molecular structure of the PFA material is as follows.

≪ PFA Molecular Structure >

Through the PFA molecular structure, it can be seen that PFA is a kind of fluoropolymer having properties similar to PTFE (polytetrafluoroethylene).

 Further, since the cup 220a and the cap 220b can be turned by turning each other in the form of a screw, a constant reaction pressure can be maintained when the electrode is manufactured. That is, the pressure in the reaction vessel 220 can be kept constant during the reaction, and the reaction solution can be prevented from escaping to the outside.

The copper electrode 230 is reacted with the reaction solution and heated by the hot plate 210 for 16 hours. When the hot plate 210 is maintained at 100 ° C, the internal temperature of the reaction vessel 220 can be maintained at 41 to 42 ° C.

6 and 7, the temperature applied to the PFA container 220 varies depending on the position of the PFA container 220 on the hot plate 210 When the temperature is applied, the first position is 74 ° C, the third position is 99 ° C, and the fifth position is 76 ° C), and the change of the current value according to the concentration of hydrogen peroxide is as follows.

Referring to FIG. 7, it can be seen that the abscissa of the graph represents the concentration of hydrogen peroxide (ppm), and the ordinate represents the measured current value (A).

Specifically, the graphs show that the current values according to the hydrogen peroxide concentration measured at the copper electrodes (230 in FIG. 5) heated at the first, fourth and fifth positions of the hot plate 210 are similar to each other Able to know. However, in the case of the copper electrode (230 in FIG. 5) heated at the third position of the hot plate 210, the hydrogen peroxide concentration and the current value are almost linearly proportional, and when heated at positions 1, 4 and 5 It can be seen that it is different. Thus, it can be seen that the current value per hydrogen peroxide concentration is influenced by the position of the copper electrode (230 in FIG. 5) on the hot plate 210.

Referring again to FIG. 4, after the copper electrode 230 is reacted according to S300, a cooling process is performed (S310).

Specifically, the copper electrode 230 is heated at a temperature of 41 to 42 ° C. for 16 hours, and the copper oxide nanoflow electrode can be crystallized through a process of cooling the copper electrode 230 again. That is, a copper oxide nanoflow electrode in the form of a black film can be obtained through a cooling process.

After the cooling process, a cleaning process is performed (S320). Specifically, by performing the cleaning process, the impurities generated in the cooling process can be removed.

When the cleaning process is completed, a black film-like copper oxide nanoflow electrode is formed (S330).

Specifically, since the copper oxide nanoflow electrode has a large surface area and is chemically stable, the current value measured at the copper oxide nanoflow electrode is linearly proportional to the hydrogen peroxide concentration range (100 to 1000 ppm) Experimental examples thereof will be described later.

Referring to FIGS. 8 to 11, the change of the copper oxide nanoflow electrode according to the reaction time in S300 of FIG. 4 can be observed.

In FIG. 8, when the reaction time is 12 hours, it can be seen that the shape of the copper oxide nanoflow electrode is not uniform and the density is low.

In contrast, in FIG. 9, when the reaction time is 16 hours, the uniformity and density of the copper oxide nanoflow electrode are remarkably improved as compared with when the reaction time is 12 hours.

In FIG. 10, it was also found that the uniformity and density of the copper oxide nanoflow electrode were improved when the reaction time was increased to 20 hours or more (20 hours, 28 hours, 48 hours) have. That is, since the copper oxide nanoflow electrode according to the embodiment of the present invention has remarkably improved uniformity and density from the time when the reaction time is increased to 16 hours or more, it has a critical value have.

11 is a graph showing a current value of hydrogen peroxide concentration measured using the copper oxide nanoflower electrode of FIG.

Referring to FIG. 11, in detail, since the time required for the reduction current value to stabilize at each concentration is maximum 300 seconds, a reduction current value when 300 seconds is consumed at each concentration is drawn as a graph, And the test was carried out in a state where it was fixed at 0.3V. 11, the abscissa of the graph represents the concentration of hydrogen peroxide (ppm), and the ordinate represents the current value (A).

11, the current values measured at 100 ppm, 200 ppm, 400 ppm, 600 ppm, 800 ppm, and 1000 ppm increase linearly with increasing hydrogen peroxide concentration. It can be seen that, of course, it does not increase in proportion but increases almost linearly. This linearity is not observed in a concentration range of less than 100 ppm or more than 1000 ppm, thereby confirming that the concentration has a critical value in a concentration range of 100 to 1000 ppm. In addition, the current value measured at each concentration shows a reduction current value of 15 to 70 μA, which is a current value measured when 300 seconds elapsed at each concentration.

In the case of the present invention, the experiment of FIG. 11 was conducted under the above limited conditions (time = 300 seconds, potential = -0.3 V), but the present invention is not limited thereto. That is, the time or potential can be conducted under conditions different from the above conditions.

Through the method (2) of manufacturing a working electrode of a hydrogen peroxide measurement sensor according to an embodiment of the present invention, a copper oxide nanoflower electrode having a critical value within a reaction time of 16 hours or more and a hydrogen peroxide concentration of 100 to 1000 ppm have.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You will understand. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (10)

A reference electrode;
A counter electrode; And
And a working electrode comprising a copper oxide nanoflow electrode,
Wherein the copper oxide nanoflow electrode comprises a copper oxide electrode and a polyimide tape layer formed on one surface of the copper oxide electrode. The method according to claim 1,
And a measuring unit for measuring the concentration of hydrogen peroxide contained in the solution through the working electrode,
In the measurement unit, a current value for each concentration of hydrogen peroxide contained in the solution is stored,
Wherein the concentration of the hydrogen peroxide is 100 to 1000 ppm. 3. The method of claim 2,
Wherein the measured current value is proportional to the hydrogen peroxide concentration. 3. The method of claim 2,
Wherein the solution contains an enzyme. The method according to claim 1,
Wherein the reference electrode comprises an Ag / Agcl electrode. The method according to claim 1,
The potential of the working electrode is adjusted based on the potential of the reference electrode,
A current flows between the working electrode and the counter electrode,
Wherein the counter electrode comprises a platinum electrode. A reference electrode including an Ag / Agcl electrode;
A counter electrode including a platinum electrode;
A working electrode comprising a copper oxide nanoflow electrode; And
And a measuring unit for measuring the concentration of hydrogen peroxide contained in the solution through the working electrode,
In the measurement unit, a current value for each concentration of hydrogen peroxide contained in the solution is stored,
The concentration of the hydrogen peroxide is 100 to 1000 ppm,
Wherein the copper oxide nanoflow electrode comprises a copper oxide electrode and a polyimide tape layer formed on the copper oxide electrode. In a PFA (Perfluoroalkoxy) vessel, copper electrode and NaOH solution for 16 hours or more,

A reaction process in which a solution is reacted is carried out,
After the reaction process is performed, a cooling process is performed,
And forming a copper oxide nanoflow electrode through a cleaning process after the cooling process. 9. The method of claim 8,
Wherein the temperature of the PFA vessel is maintained at 41 to 42 DEG C during the reaction process. 9. The method of claim 8,
Further comprising forming a polyimide tape layer on one side of the copper electrode.

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