KR20230144783A - Alcohol Sensor Based on Metal Catalyst and Wearable Device Comprising the Same - Google Patents

Abstract

Disclosed is a metal catalyst-based alcohol sensor and a wearable device including the same.
An alcohol sensor according to an embodiment of the present invention includes one or a plurality of electrodes for detecting the alcohol concentration; and a metal catalyst layer for a reaction to acquire electrons through a reaction with an alcohol component contained in the fluid sample to detect the concentration of alcohol contained in the fluid sample, the metal catalyst layer located on one side of the electrode. may include.

Description

Alcohol sensor based on metal catalyst and wearable device including same {Alcohol Sensor Based on Metal Catalyst and Wearable Device Comprising the Same}

The present invention relates to an alcohol sensor that measures alcohol content using a metal catalyst and a wearable device including the same.

The content described in this section simply provides background information on embodiments of the present invention and does not constitute prior art.

Due to Korea's high per capita annual alcohol consumption (8.5 L) in 2018, drinking-related social costs are approaching KRW 9.4 trillion, including KRW 235.1 billion in professional treatment costs for alcohol-related diseases (mental and behavioral disorders, liver disease, etc.). .

Referring to Figure 1 (a), alcohol is not digested and is absorbed into cells or body tissues through plasma. After drinking, 20% of the alcohol consumed is absorbed from the stomach and 80% of the alcohol is absorbed from the intestines.

95% of alcohol absorbed into the body is decomposed in the liver, 4% is excreted as alcohol itself through respiratory gas, saliva, tears, urine, etc., and finally, 1% is excreted directly through the skin (transdermal). Alcohol gas released directly from the transdermis is small (several ppm) and released slowly, but is highly correlated with blood alcohol concentration (BAC).

Breathing breath alcohol measuring devices, which are widely used to determine drinking, are fuel cell-based, have a short measurement time, and are widely used as there are many portable devices.

The fuel cell-based alcohol sensor in (b) of Figure 1 may cause fouling due to humidity (reduced sensitivity), signal drift may occur over time (reduced reliability and accuracy), and low level There is a problem that the possibility of detecting the amount of alcohol consumed is low. The enzyme-based alcohol sensor shown in Figure 1 (c) has problems such as short service life, low stability, and conductivity compared to the fuel cell type.

However, these alcohol sensors are not suitable for monitoring drinking status because errors occur due to gargling containing alcohol and continuous measurement is not possible. As alcohol monitoring sensors are required to determine whether a user is drinking and for medical and healthcare purposes, an alcohol monitoring sensor capable of continuous measurement is needed.

The present invention provides a metal catalyst-based alcohol sensor incorporating an alloy metal catalyst and an ionic liquid to be implemented in an alcohol monitoring sensor capable of continuous measurement based on extracorporeal gases generated in the transdermis, and a wearable device including the same. There is a main purpose.

According to one aspect of the present invention, an alcohol sensor for achieving the above object includes one or a plurality of electrodes for detecting the alcohol concentration; and a metal catalyst layer for a reaction to acquire electrons through a reaction with an alcohol component contained in the fluid sample to detect the concentration of alcohol contained in the fluid sample, the metal catalyst layer located on one side of the electrode. may include.

In addition, according to another aspect of the present invention, a wearable device for achieving the above object includes one or a plurality of electrodes, and an alcohol component contained in the fluid sample to detect the alcohol concentration contained in the fluid sample. An alcohol sensor comprising a metal catalyst layer for a reaction to acquire electrons through a reaction, and a metal catalyst layer located on one side of the electrode; an alcohol concentration measuring unit electrically connected to the electrode and measuring the alcohol concentration based on changes in electrical characteristics detected from the electrode; a memory for storing the measured alcohol concentration; and a processor that compares the measured alcohol concentration with a predetermined reference value and performs an operation to deliver a message about the alcohol concentration to the outside.

As described above, the present invention has the effect of implementing a highly sensitive sensor.

Additionally, the present invention has the effect of improving the detection limit of the sensor.

Additionally, the present invention has the effect of extending the service life of the sensor.

Additionally, the present invention has the effect of improving alcohol gas (vapor) collection performance.

Figure 1 is an exemplary diagram for explaining a conventional alcohol measurement method.
Figure 2 is a diagram schematically showing an alcohol sensor according to a first embodiment of the present invention.
Figure 3 is a diagram schematically showing an alcohol sensor according to a second embodiment of the present invention.
Figure 4 is a diagram showing the structure of an alcohol sensor according to an embodiment of the present invention.
Figure 5 is a diagram for explaining a metal catalyst of an alcohol sensor according to an embodiment of the present invention.
Figure 6 is a diagram for explaining the ionic liquid of the alcohol sensor according to an embodiment of the present invention.
Figure 7 is a flowchart for explaining the manufacturing process of an alcohol sensor according to an embodiment of the present invention.
8 and 9 are diagrams for explaining an example of manufacturing an alcohol sensor according to an embodiment of the present invention.
10 to 15 are diagrams for explaining the test method and test results of an alcohol sensor according to an embodiment of the present invention.
Figure 16 is a block diagram schematically showing a wearable device including an alcohol sensor according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted. In addition, preferred embodiments of the present invention will be described below, but the technical idea of the present invention is not limited or restricted thereto, and of course, it can be modified and implemented in various ways by those skilled in the art. Hereinafter, a metal catalyst-based alcohol sensor and a wearable device including the same proposed in the present invention will be described in detail with reference to the drawings.

Figure 2 is a diagram schematically showing an alcohol sensor according to a first embodiment of the present invention.

The alcohol sensor 100 according to the first embodiment of the present invention includes a base 110, side structures 120 and 122, electrode portions 130, 132, and 134, and a metal catalyst 140. The alcohol sensor 100 of FIG. 2 is according to one embodiment, and not all blocks shown in FIG. 2 are essential components. In other embodiments, some blocks included in the alcohol sensor 100 may be added, changed, or deleted. It can be.

The alcohol sensor 100 refers to a sensor for measuring alcohol in the body.

When a fluid sample is input, the alcohol sensor 100 according to the first embodiment measures alcohol in the fluid sample using a metal catalyst and an electrode connected to the metal catalyst.

Base 110 refers to a structure that supports the lower side of the alcohol sensor 100. The base 110 is made of an insulating material.

The side structures 120 and 122 are coupled to the base 110, are formed on both ends of the base 110, and are structures for forming a space into which a fluid sample is introduced.

The side structures 120 and 122 may be formed of two different structures, but are not necessarily limited thereto, and may be one structure connected to each other.

The electrode units 130, 132, and 134 perform an operation of measuring alcohol using an electrochemical signal depending on the concentration of alcohol reacted with the metal catalyst.

The electrode units 130, 132, and 134 include one or at least two electrodes and are disposed on the upper side of the base 110.

The electrode units 130, 132, and 134 are shown as a third electrode system consisting of a working electrode (130), a counter electrode (132), and a reference electrode (134), but are limited to this. This does not mean that it can be configured as a second electrode system consisting of a working electrode and a reference electrode. Here, the working electrode refers to an electrode for actually measuring alcohol, and the counter electrode refers to an electrode that applies a potential and allows current to flow. Additionally, the reference electrode refers to an electrode that holds the standard for the potential applied to the working electrode.

A metal catalyst 140 is stacked on the upper side of the working electrode among the electrode units 130, 132, and 134.

The metal catalyst layer includes a metal catalyst 140 for a reaction to acquire electrons through reaction with an alcohol component contained in the fluid sample, and a support that fixes the metal catalyst so that the metal catalyst 140 can come into contact with the fluid sample.

The metal catalyst 140 refers to a catalyst that reacts with alcohol in a fluid sample.

The metal catalyst 140 is connected to the working electrode and reacts with the alcohol in the fluid sample so that an electrochemical signal according to the alcohol component can be measured at the working electrode.

The metal catalyst 140 may be formed of a single metal material. The metal catalyst 140 may include platinum (Pt) or an alloy containing platinum.

Meanwhile, the metal catalyst 140 may be formed of an alloy material in which at least one material is combined.

The metal catalyst 140 may be formed including platinum (Pt) at a ratio within the range of 10 to 100 at% (atomic percent).

The metal catalyst 140 is at least one of platinum (Pt), nickel (Ni), ruthenium (Ru), cobalt (Co), palladium (Pd), iridium (Ir), chromium (Cr), and rhodium (Rh). It can be formed in a form containing an alloy in which (elements) are combined.

In addition, the metal catalyst 140 is at least one of platinum (Pt), nickel (Ni), ruthenium (Ru), cobalt (Co), palladium (Pd), iridium (Ir), chromium (Cr), and rhodium (Rh). It can be formed in a form that includes a carbon-supported alloy in which an alloy of materials (elements) is combined and supported on carbon (C).

When the metal catalyst 140 is formed of an alloy material containing platinum (Pt), the material combined with platinum (Pt) may be at least one of a metallic material, a non-metallic material, or a synthetic material combining a metallic material and a non-metallic material. there is.

The metal catalyst 140 may be formed on the support to increase the surface area with the fluid sample. Here, the support is formed of a carbon-based material. The support may be formed of a carbon-based material such as carbon black, carbon nanotube, graphene, graphene oxide, or graphite.

Figure 3 is a diagram schematically showing an alcohol sensor according to a second embodiment of the present invention.

The alcohol sensor 100 according to the second embodiment of the present invention includes a base 110, side structures 120, 122, electrode parts 130, 132, 134, a metal catalyst 140, and an ionic liquid 150. and a transmission membrane 160. The alcohol sensor 100 of FIG. 3 is according to one embodiment, and not all blocks shown in FIG. 3 are essential components. In other embodiments, some blocks included in the alcohol sensor 100 may be added, changed, or deleted. It can be.

The alcohol sensor 100 refers to a sensor for measuring alcohol in the body.

In the alcohol sensor 100 according to the second embodiment, when a fluid sample is introduced, the fluid sample and the ionic liquid are mixed, and the alcohol in the mixed liquid reacts with the metal catalyst to produce alcohol through an electrode connected to the metal catalyst. Measure. Here, the fluid sample is preferably an extracorporeal gas generated from the transdermis, but is not necessarily limited thereto, and may be a variety of gases discharged from the body, including alcohol components.

Extracorporeal gas generated from the transdermis is a gas that vaporizes through the skin of a drunk person's body, and the gas contains alcohol.

The alcohol sensor 100 of FIG. 3 includes the same base 110, side structures 120 and 122, electrode units 130, 132 and 134, and metal catalyst 140 as shown in FIG. 2. Accordingly, overlapping descriptions of the components shown in FIG. 2 will be omitted.

The permeable membrane 160 serves to filter the fluid sample introduced into the alcohol sensor 100 by selectively transmitting all or part of the gas component of the gaseous fluid sample generated in the transdermis.

The transmission membrane 160 is combined with the side structure. The transmission film 160 is formed in parallel and opposite to the base 110 with a portion of its surface in contact with the upper surfaces of the side structures 120 and 122. The transmission membrane 160 is preferably formed to have a thickness between 10 and 100 μm.

The transmission membrane 160 may be formed of polymer or co-polymer.

For example, the permeable membrane 160 is made of hydrophilic aliphatic polyether, hydrophobic aliphatic polyether, polyester, polyethylene, polytetrafluoroethylene, It may be formed by including at least one selected from the group consisting of thermoplastic olefin and thermoplastic polyurethane.

The ionic liquid 150 collects the fluid sample that has passed through the permeable membrane 160 and exists in a liquid ion state. The ionic liquid 150 is mixed with the fluid sample (gas) that has passed through the permeable membrane 160 and serves to create a sensing environment so that the alcohol contained in the fluid sample (gas) reacts with the metal catalyst 140. .

The ionic liquid 150 is filled in the space formed by the structure surrounded by the base 110, the side structures 120 and 122, and the permeable membrane 160.

The ionic liquid 150 according to this embodiment includes imidazole, pyrrolidinium, pyridinium, piperidinium, ammonium, phosphonium, and sulfur. It may be from at least one series of sulphonium.

If the ionic liquid 150 is an imidazole-based ionic liquid 150, the imidazole-based ionic liquid 150 is 1-butyl-3-methylimidazolium tetrafluoroborate (1-Butyl-3- methylimidazolium tetrafluoroborate), 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-ethyl-3-methylimidazolium 1-Ethyl-3-methylimidazolium dicyanamide, 1-Butyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium hexafluoride It may include 1-Butyl-3-methylimidazolium hexafluorophosphate, 1-decyl-3-methylimidazolium chloride, etc.

Meanwhile, when the ionic liquid 150 is a pyrrolidinium-based ionic liquid 150, the pyrrolidinium-based ionic liquid 150 is 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl sulfur). It may include 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide).

On the other hand, when the ionic liquid 150 is pyridinium-based, the pyridinium-based ionic liquid 150 is 1-butyl-4-methylpyridinium tetrafluoroborate (1-Butyl-4 -methylpyridinium tetrafluoroborate).

Meanwhile, when the ionic liquid 150 is a piperidinium-based ionic liquid 150, the piperidinium-based ionic liquid 150 is 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfur). It may include ponyl)imide (1-Butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide).

On the other hand, when the ionic liquid 150 is an ammonium-based ionic liquid 150, the ammonium-based ionic liquid 150 may include tetramethylammonium acetate and tributylmethylammonium chloride. You can.

Meanwhile, when the ionic liquid 150 is phosphonium-based, the phosphonium-based ionic liquid 150 may include trihexyltetradecylphosphonium dicyanamide.

On the other hand, when the ionic liquid 150 is a sulfonium-based ionic liquid 150, the sulfonium-based ionic liquid 150 is triethylsulfonium bis(trifluoromethylsulfonyl)imide (Triethylsulfonium bis( It may include trifluoromethylsulfonyl)imide).

In the above-described embodiment, the structure of the alcohol sensor 100 for accommodating the fluid sample and the ionic liquid was presented, including a side structure, a base at the bottom, and a permeable membrane at the top. The configuration of the side structures and base need not be limited to these structures. For example, the side structure and the base may be formed from a single material or integrally combined. Additionally, it is also possible to form a groove inside the base or to form the base in a streamlined shape to accommodate an ionic liquid or fluid sample.

Figure 4 is a diagram showing the structure of an alcohol sensor according to an embodiment of the present invention.

The alcohol sensor structure in FIG. 4 is a transdermal alcohol sensor manufactured based on the alcohol sensor 100 according to the second embodiment.

The alcohol sensor 100 has a working electrode 130, a counter electrode 132, and a reference electrode 134 based on a third electrode system formed on the base 110.

A metal catalyst 140 is stacked on the upper side of the working electrode 130.

The side structure 120 and the top cover 162 are formed in a hollow shape at the center of the rectangular structure and are stacked on the base 110.

The electrode portions 130, 132, and 134 and the metal catalyst 140 are exposed within the hollow of the side structure 120 and the top cover 162.

The space formed by the base 110 and the side structure 120 is filled with the ionic liquid 150, and a transmission membrane ( 160) is formed.

Figure 5 is a diagram for explaining a metal catalyst of an alcohol sensor according to an embodiment of the present invention.

The metal catalyst 140 controls the electrochemical reaction according to the alcohol concentration contained in the input sample (fluid sample).

Referring to FIG. 5, the metal catalyst 140 may include at least one selected from the group consisting of platinum (Pt) and alloys thereof, or a compound of a base metal and platinum (Pt).

The alloy constituting the metal catalyst 140 is PtM, where M is nickel (Ni), ruthenium (Ru), cobalt (Co), palladium (Pd), iridium (Ir), chromium (Cr), and rhodium (Rh). ) may include at least one selected from ). In PtM, the atomic ratio of M relative to platinum (Pt) is preferably 10 to 100.

The metal catalyst 140 has a structural effect as it is formed using an alloy containing platinum (Pt). That is, in the alloy-based metal catalyst 140, the bond distance between platinum (Pt) and platinum (Pt) changes due to a change in the lattice parameter.

As it is formed using an alloy containing platinum (Pt), it has an electrical effect. In other words, the alloy-based metal catalyst 140 can improve activity and selectivity and reduce the binding energy of platinum (Pt) and carbon monoxide (CO). Additionally, the alloy-based metal catalyst 140 can destroy the C-C bond of alcohol.

Referring to FIG. 5, the metal catalyst 140 may be formed on a support to increase the surface area with the fluid sample and improve catalyst performance. Here, the support is formed of a carbon-based material. The support may be formed of a carbon-based material such as carbon black, carbon nanotube, graphene, graphene oxide, or graphite.

Figure 6 is a diagram for explaining the ionic liquid of the alcohol sensor according to an embodiment of the present invention.

Figure 6 shows various ionic liquids. Ionic liquids are substances that are composed of cations and anions and exist in a liquid state at room temperature.

Figure 7 is a flowchart for explaining the manufacturing process of an alcohol sensor according to an embodiment of the present invention.

Step S1110 prepares a permeable membrane for selectively permeating the gas of the fluid sample.

Step S1120 prepares a metal catalyst for a reaction that acquires electrons through reaction with the alcohol component contained in the fluid sample.

In step S1130, the prepared metal catalyst is stacked and combined on the working electrode.

In step S1140, the electrode is fixed to the base, a hollow is formed in the side structure parallel to the base, and the ionic liquid is injected into the hollow.

In step S1150, a sensor is manufactured by adsorbing the manufactured transparent membrane to prevent bubbles from being generated.

In Figure 7, each step is described as being executed sequentially, but it is not necessarily limited to this. In other words, the steps shown in FIG. 7 may be applied by modifying and executing one or more steps in parallel, so FIG. 7 is not limited to a time series order.

8 and 9 are diagrams for explaining an example of manufacturing an alcohol sensor according to an embodiment of the present invention.

The alcohol sensor 100 according to the present invention will be described in more detail through examples below. Since these examples are only for illustrating the present invention, it is obvious to those skilled in the art that the scope of the present invention should not be construed as limited by these examples.

<Example 1>

1. Gas permeable membrane (Sensing membrane) manufacturing

- Dissolve Lubrizol's HP-60D-20 at a concentration of 400 mg/mL of tetrahydrofuran, then pour 300 μL into a glass ring with a diameter of 10 mm under the conditions of a temperature of 20°C and a relative humidity of 10% or less. Dry overnight.

2. Metal catalyst cocktail mixing

- In a 10 mL vial, add 8 mg of metal catalyst platinum (Pt), 1000 μL of H ₂ O (tertiary distilled water), 50 μL of Nafion 5%, and 500 μL of isopropyl alcohol (IPA). Ultrasonication for 30 minutes.

3. Metal catalyst dispensing and drying

- Dispense the metal catalyst cocktail using a semi-auto dispenser at 3~4 psi, 0.03 sec. After dispensing 6 times on the working electrode of the electrode, dry for 10 minutes at 60°C and relative humidity of 20% or less.

4. Fabrication of alcohol sensor incorporating metal catalyst and ionic liquid

- Make a groove with a diameter of 2 mm on a 1 mm thick waterproof double-sided tape, attach it so that the working electrode of the prepared electrodes is located in the exact center of the groove, and then apply the ionic liquid 1-butyl-3-methylimidazolium 1-butyl. Fill 15 μL of 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. Afterwards, the sensor is manufactured by adsorbing the prepared gas permeable membrane to prevent bubbles from being generated.

<Example 2>

In the gold catalyst cocktail mixing of Example 1-2 (metal catalyst cocktail mixing), the same procedure was performed except that 12 mg of platinum nickel (PtNi) was added in place of platinum (Pt).

<Example 3>

1. Gas permeable membrane (Sensing membrane) manufacturing

- After dissolving Lubrizol's HP-60D-20 at a concentration of 400 mg/mL of tetrahydrofuran, add 250 μL to a glass ring with a diameter of 8 mm under the conditions of a temperature of 20 ℃ and a relative humidity of 10% or less. Dry overnight.

2. Metal catalyst cocktail mixing

- 14 mg of platinum-tin alloy (C/PtSn) supported on carbon (C) in a 10 mL vial, 800 μL of H ₂ O (tertiary distilled water), 50 μL of Nafion 5%, Add 400 μL of isopropyl alcohol (IPA) and sonicate for 30 minutes.

3. Metal catalyst dispensing and drying

- Dispense the metal catalyst cocktail using a semi-auto dispenser at 3~4 psi, 0.03 sec. After dispensing 6 times on the working electrode of the electrode, dry for 10 minutes at 60°C and relative humidity of 20% or less.

4. Fabrication of alcohol sensor incorporating metal catalyst and ionic liquid

- Make a groove with a diameter of 2 mm on a 1 mm thick waterproof double-sided tape, attach it so that the working electrode of the prepared electrodes is located in the exact center of the groove, and then apply the ionic liquid 1-butyl-3-methylimidazolium tetrafluoro. Fill 15 μL of borate (1-Butyl-3-methylimidazolium tetrafluoroborate). Afterwards, the sensor is manufactured by adsorbing the prepared gas permeable membrane to prevent bubbles from being generated.

<Example 4>

In the gold catalyst cocktail mixing of Example 3-2 (metal catalyst cocktail mixing), platinum-nickel supported on carbon (C) replaced the carbon supported platinum-tin alloy (C/PtSn) supported on carbon (C). The same procedure was performed except that 12 mg of alloy (C/PtNi) was added.

<Example 5>

In the gold catalyst cocktail mixing of Example 3-2 (metal catalyst cocktail mixing), platinum-chromium supported on carbon (C) replaced the carbon supported platinum-tin alloy (C/PtSn) supported on carbon (C). The same procedure was performed except that 12 mg of alloy (C/PtCr) was added.

<Example 6>

1. Gas permeable membrane (Sensing membrane) manufacturing

- Dissolve Lubrizol's HP-60D-20 at a concentration of 400 mg/mL of tetrahydrofuran, then pour 300 μL into a glass ring with a diameter of 6 mm under the conditions of a temperature of 20°C and a relative humidity of 10% or less. Dry overnight.

2. Metal catalyst cocktail mixing

- In a 10 mL vial, 14 mg of platinum-nickel (C/PtNi) supported on carbon (C), 740 μL of H ₂ O (tertiary distilled water), 60 μL of Nafion 5%, and isopropyl alcohol Add 400 μL of (isopropyl alcohol, IPA) and sonicate for 30 minutes.

3. Metal catalyst dispensing and drying

- Dispense the metal catalyst cocktail using a semi-auto dispenser at 3~4 psi, 0.03 sec. After dispensing 6 times on the working electrode of the electrode, dry for 10 minutes at 60°C and relative humidity of 20% or less.

4. Fabrication of alcohol sensor incorporating metal catalyst and ionic liquid

- Make a groove with a diameter of 2 mm on a 1 mm thick waterproof double-sided tape, attach it so that the working electrode among the prepared electrodes is located in the exact center of the groove, and then apply the ionic liquid 1-butyl-3-methylimidazolium bis(tri). Fill 10 μL of 1-butyl-3-methylimidazolium bis(trifluoromethylsolfony)imide). Afterwards, the sensor is manufactured by adsorbing the prepared gas permeable membrane to prevent bubbles from being generated.

<Example 7>

Ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (1-butyl-3-methylimidazolium bis(trifluoromethylsolfony)imide) of Example 5-4 (preparation of alcohol sensor incorporating metal catalyst and ionic liquid) ) The same procedure was performed except that 13 μL of 1-ethyl-3-methylimidazolium dicyanamide was added instead.

<Example 8>

Ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (1-butyl-3-methylimidazolium bis(trifluoromethylsolfony)imide) of Example 5-4 (preparation of alcohol sensor incorporating metal catalyst and ionic liquid) ) The same procedure was performed except that 14 μL of 1-Butyl-4-methylpyridinium tetrafluoroborate was added instead.

<Example 9>

Ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (1-butyl-3-methylimidazolium bis(trifluoromethylsolfony)imide) of Example 5-4 (preparation of alcohol sensor incorporating metal catalyst and ionic liquid) ) The same procedure was performed except that 10 μL of tributylmethylammonium chloride was added instead.

<Example 10>

Ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (1-butyl-3-methylimidazolium bis(trifluoromethylsolfony)imide) of Example 5-4 (preparation of alcohol sensor incorporating metal catalyst and ionic liquid) ) The same procedure was performed except that 15 μL of trihexyltetradecylphosphonium dicyanamide was added instead.

<Example 11>

1. Gas permeable membrane (Sensing membrane) manufacturing

- After dissolving Lubrizol's SG-80A at a concentration of 320 mg/mL of tetrahydrofuran, pour 200 μL into a glass ring with a diameter of 6 mm and overheat at a temperature of 20°C and a relative humidity of 10% or less. Dry overnight.

2. Metal catalyst cocktail mixing (Sensing membrane)

- 15 mg of metal catalyst containing platinum-ruthenium alloy (C/PtRu) supported on carbon (C) in a 10 mL vial, 700 μL of H ₂ O (tertiary distilled water), Nafion Add 40 μL of 5% and 500 μL of isopropyl alcohol (IPA) and sonicate for 30 minutes.

3. Metal catalyst dispensing and drying

- Dispense the metal catalyst cocktail using a semi-auto dispenser at 3~4 psi, 0.03 sec. After dispensing 6 times on the working electrode of the electrode, dry for 5 minutes at 60°C and relative humidity of 20% or less.

4. Fabrication of alcohol sensor incorporating metal catalyst and ionic liquid

- Make a groove with a diameter of 2 mm on a 1 mm thick waterproof double-sided tape, attach it so that the working electrode of the prepared electrodes is located in the exact center of the groove, and then apply the ionic liquid 1-butyl-1-methylpyrrolidinium bis(tri). Fill 13 μL of 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. Afterwards, the sensor is manufactured by adsorbing the prepared gas permeable membrane to prevent bubbles from being generated.

<Example 12>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), platinum supported on carbon (C) was used instead of the carbon supported platinum-ruthenium alloy (C/PtRu). The same procedure was performed except that cobalt alloy (C/PtCo) was added to 13 mg.

<Example 13>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), platinum supported on carbon (C) was used instead of the carbon supported platinum-ruthenium alloy (C/PtRu). The same procedure was performed except that 15 mg of palladium alloy (C/PtPd) was added.

<Example 14>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), platinum supported on carbon (C) was used instead of the carbon supported platinum-ruthenium alloy (C/PtRu). The same procedure was performed except that 10 mg of iridium alloy (C/PtIr) was added.

<Example 15>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), platinum supported on carbon (C) was used instead of the carbon supported platinum-ruthenium alloy (C/PtRu). The same procedure was performed except that 10 mg of nickel alloy (C/PtNi) was added.

<Example 16>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), platinum supported on carbon (C) was used instead of the carbon supported platinum-ruthenium alloy (C/PtRu). The same procedure was performed except that 13 mg of chromium alloy (C/PtNi) was added.

<Example 17>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), instead of the carbon supported platinum-ruthenium alloy (C/PtRu) supported on carbon (C), graphene oxide was used. The same procedure was performed except that 20 mg of platinum-nickel alloy (GO/PtNi) was added.

<Example 18>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), instead of the carbon supported platinum-ruthenium alloy (C/PtRu) supported on carbon (C), graphene oxide was used. The same procedure was performed except that 20 mg of platinum-ruthenium alloy (GO/PtNi) was added.

<Example 19>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), instead of the carbon supported platinum-ruthenium alloy (C/PtRu) supported on carbon (C), graphene oxide was used. The same procedure was performed except that 20 mg of platinum-rhodium alloy (GO/PtRh) was added.

<Example 20>

In the gold catalyst cocktail mixing of Example 11-2 (metal catalyst cocktail mixing), instead of the carbon supported platinum-ruthenium alloy (C/PtRu) supported on carbon (C), graphene oxide was used. The same procedure was performed except that 20 mg of platinum-ruthenium alloy (GO/PtRu) was added.

<Example 21>

1. Manufacturing of gas permeable membrane (Sensing membrane)

- Dissolve Lubrizol's HP-60D-30 at a concentration of 320 mg/mL of tetrahydrofuran, then pour 200 μL into a glass ring with a diameter of 6 mm under the conditions of a temperature of 20°C and a relative humidity of 10% or less. Dry overnight.

2. Metal catalyst cocktail mixing (Sensing membrane)

- In a 10 mL vial, 20 mg of metal catalyst containing carbon-supported platinum-nickel alloy (CNT/PtNi) supported on carbon nanotubes, 700 μL of H ₂ O (tertiary distilled water), Nafion ( Add 40 μL of Nafion 5% and 500 μL of isopropyl alcohol (IPA) and sonicate for 30 minutes.

3. Metal catalyst dispensing and drying

- Dispense the metal catalyst cocktail using a semi-auto dispenser at 3~4 psi, 0.03 sec. After dispensing 3 times on the working electrode of the electrode, dry for 5 minutes at 60°C and relative humidity of 20% or less.

4. Fabrication of alcohol sensor incorporating metal catalyst and ionic liquid

- Make a groove with a diameter of 2 mm on a 1 mm thick waterproof double-sided tape, attach it so that the working electrode of the prepared electrodes is located in the exact center of the groove, and then add the ionic liquid 1-butyl-4-methylpyridinium tetrafluoroborate. Fill 10 μL of (1-Butyl-4-methylpyridinium tetrafluoroborate). Afterwards, the sensor is manufactured by adsorbing the prepared gas permeable membrane to prevent bubbles from being generated.

10 to 15 are diagrams for explaining the test method and test results of an alcohol sensor according to an embodiment of the present invention.

<Experiment method>

The fluid sample containing alcohol used in the experiment of the transdermal alcohol sensor uses extracorporeal gas generated from the transdermis.

The measurement results of the transdermal alcohol sensor can be compared with the blood alcohol concentration and transdermal measurement results in the following manner.

Referring to FIG. 10, assuming that 0.1 g of alcohol is contained in 100 ml of blood, a blood alcohol concentration of 0.1% can be calculated as 0.1% BAC = 80 mg/100ml when calculated using the alcohol specific gravity (0.8 g/ml). Therefore, if 80 mg/100ml is converted to ppm, it can be calculated as 800 ppm.

<Experiment results and performance evaluation>

Figure 11 (a) shows alcohol sensitivity to changes in current output from the electrode according to alcohol gas concentration over time through a transdermal alcohol sensor.

Figure 11 (b) shows an alcohol calibration curve showing the correlation between currents for each alcohol gas concentration.

Figure 12 shows experimental results regarding the service life of a transdermal alcohol sensor capable of continuous monitoring. It can be confirmed that the alcohol measurement performance is maintained until about 40 days have passed.

Figure 13 shows the evaluation of the humidity effect of the alcohol sensor for transdermal measurement in which a metal catalyst and an ionic liquid are introduced.

Figure 13 shows the change in current according to the change in humidity by increasing the humidity from 25% to 100% from the time the alcohol component was measured (about 1000 sec).

Figure 14 (a) shows the change in current according to the change in temperature in the transdermal alcohol sensor. Figure 14 (b) shows the change in current according to the measurement temperature during operation of the transdermal alcohol sensor. In the transdermal alcohol sensor, it can be seen that the current value increases as the temperature increases.

Figure 15 shows the evaluation of a drunken person's transdermal alcohol sensor incorporating a metal catalyst and ionic liquid.

Figure 15(a) shows the results of transdermal alcohol sensitivity of the first drunk, and Figure 15(b) shows the results of transdermal alcohol sensitivity of the second drunk. It can be seen that alcohol vapor was generated from the skin of the two drunkards 20 and 32 minutes after drinking, respectively. In the graph of FIG. 15, the dots represent the measurement results of the respiratory-type alcohol meter, and it can be seen that they show almost similar trends to the measurement results of the transdermal alcohol sensor of the present invention.

Figure 16 is a block diagram schematically showing a wearable device including an alcohol sensor according to an embodiment of the present invention.

A wearable device for continuously monitoring alcohol concentration includes one or a plurality of electrodes, and acquires electrons through a reaction with the alcohol component contained in the fluid sample to detect the alcohol concentration contained in the fluid sample. an alcohol sensor including a metal catalyst for reaction and a metal catalyst layer located on one side of the electrode; an alcohol concentration measuring unit electrically connected to the electrode and measuring the alcohol concentration based on changes in electrical characteristics detected from the electrode; a memory for storing the measured alcohol concentration; and a processor that compares the measured alcohol concentration with a predetermined reference value and performs an operation to deliver a message about the alcohol concentration to the outside.

The alcohol sensor of the wearable device further includes an insulating base and a side structure coupled to the base to confine the fluid sample. Here, the one or plurality of electrodes are disposed on the base, and the metal catalyst layer further includes a support for fixing the metal catalyst so that the metal catalyst can contact the fluid sample.

The above description is merely an exemplary explanation of the technical idea of the embodiments of the present invention, and those skilled in the art can make various modifications and modifications without departing from the essential characteristics of the embodiments of the present invention. Transformation will be possible. Accordingly, the embodiments of the present invention are not intended to limit but to explain the technical idea of the embodiment of the present invention, and the scope of the technical idea of the embodiment of the present invention is not limited by these embodiments. The scope of protection of the embodiments of the present invention should be interpreted in accordance with the claims below, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of rights of the embodiments of the present invention.

Claims (14)

In the alcohol sensor that detects the alcohol concentration of a fluid sample,
One or more electrodes for detecting the alcohol concentration; and
In order to detect the concentration of alcohol contained in the fluid sample, a metal catalyst layer located on one side of the electrode and comprising a metal catalyst for a reaction to obtain electrons through a reaction with an alcohol component contained in the fluid sample; Including, alcohol sensor. According to claim 1,
The alcohol sensor further includes an insulating base,
The one or more electrodes are disposed on the base,
The alcohol sensor is coupled to the base and further includes a side structure for confining the fluid sample. According to claim 1,
The metal catalyst layer further includes a support for fixing the metal catalyst so that the metal catalyst can come into contact with the fluid sample. According to clause 2,
The fluid sample is a gas generated from the transdermis of a person whose alcohol concentration is to be measured,
The alcohol sensor is,
a permeable membrane that selectively transmits the fluid sample and is coupled to the side structure; and
An alcohol sensor that collects the fluid sample that has passed through the permeable membrane and further includes an ionic liquid that exists in a liquid ionic state. According to clause 3,
The metal catalyst is one selected from the group consisting of platinum (Pt) and alloys thereof, or a compound of a base metal and platinum (Pt). According to clause 5,
The alloy is PtM, where M is selected from the group consisting of nickel (Ni), ruthenium (Ru), cobalt (Co), palladium (Pd), iridium (Ir), chromium (Cr) and rhodium (Rh). Contains at least one,
The support includes at least one carbon-based material selected from carbon black, carbon nanotube, graphene, graphene oxide, and graphite. An alcohol sensor, characterized in that. According to clause 6,
In the PtM, the atomic ratio of M relative to platinum is 10 to 100. According to paragraph 1,
The plurality of electrodes are,
a third electrode system including a working electrode, a counter electrode, and a reference electrode; or
An alcohol sensor comprising a second electrode system including a working electrode and a reference electrode, wherein the metal catalyst layer is formed on one surface of the working electrode. According to paragraph 4,
The permeable membrane includes a polymer or co-polymer, and the polymer or co-polymer is,
Hydrophilic aliphatic polyether, hydrophobic aliphatic polyether, polyester, polyethylene, polytetrafluoroethylene, thermoplastic olefin and thermoplastic polyurethane. An alcohol sensor comprising at least one selected from the group consisting of (thermoplastic polyurethane). According to clause 9,
The permeable membrane is,
An alcohol sensor, characterized in that it is formed opposite the base in a form in which a part of the surface is in contact with the upper side of the side structure, and has a thickness of 10 to 100 μm. According to paragraph 4,
The ionic liquid contains one cation and one anion,
The cation is selected from the group consisting of imidazole, pyrrolidinium, pyridinium, piperidinium, ammonium, phosphonium, and sulfonium. An alcohol sensor, comprising at least one of: According to paragraph 4,
The ionic liquid contains cations or anions, and the cations are,
Imidazolium-based ionic liquid, 1-Butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis(tri) 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), 1-Ethyl-3-methylimidazolium dicyanamide, 1-butyl -3-Butyl-3-methylimidazolium iodide, 1-Butyl-3-methylimidazolium hexafluorophosphate and 1-decyl- Contains at least one selected from the group consisting of 3-methylimidazolium chloride (1-decyl-3-methylimidazolium chloride),
It is a pyrrolidinium-based ionic liquid and contains 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. do or,
A pyridinium-based ionic liquid containing 1-Butyl-4-methylpyridinium tetrafluoroborate, or
It is a piperidinium-based ionic liquid and contains 1-Butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide. do or,
An ammonium-based ionic liquid containing tetramethylammonium acetate or tributylmethylammonium chloride, or
As a phosphonium-based ionic liquid, the phosphonium-based ionic liquid 150 includes trihexyltetradecylphosphonium dicyanamide, or
An alcohol sensor that is a sulfonium-based ionic liquid, characterized in that it contains triethylsulfonium bis(trifluoromethylsulfonyl)imide. In a wearable device for continuously monitoring alcohol concentration,
One or a plurality of electrodes, and a metal catalyst for a reaction to obtain electrons through a reaction with an alcohol component contained in the fluid sample to detect the concentration of alcohol contained in the fluid sample, the electrode An alcohol sensor including a metal catalyst layer located on one side of;
an alcohol concentration measuring unit electrically connected to the electrode and measuring the alcohol concentration based on changes in electrical characteristics detected from the electrode;
a memory for storing the measured alcohol concentration; and
A wearable device comprising a processor that compares the measured alcohol concentration with a predetermined reference value and performs an operation to deliver a message about the alcohol concentration to the outside. According to clause 14,
The alcohol sensor includes an insulating base,
In combination with the base, it further includes a side structure for confining the fluid sample,
The one or more electrodes are disposed on the base,
The metal catalyst layer further includes a support for fixing the metal catalyst so that the metal catalyst can come into contact with the fluid sample.

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