COLORIMETRIC SENSOR MATERIAL FOR DETECTING HYDROGEN SULFIDE GAS, WHICH INCLUDES ONE-DIMENSIONAL POLYMER NANOFIBER COUPLED TO LEAD ACETATE PARTICLES OBTAINED BY HIGH TEMPERATURE STIRRING AND QUENCHING, AND METHOD OF THE SAME

Abstract

Disclosed are polymer nanofiber sensors for detecting gas, which generates visible color change although a specific gas having a concentration of less than 1 ppm is exposed to the sensor in a short time, in which it is impossible to detect the gas using existing colorimetric sensors, through securing high surface area and porosity, and a method of the same.

Claims

1. A polymer nanofiber sensor for gas indication comprising: a polymer nanofiber; and a dye material coupled to the polymer nanofiber, wherein the dye material is coupled to an inner part and a surface of the polymer nanofiber through a melting process in which the dye material is stirred at a high temperature of more than melting point and a quenching process in which the melted dye material is changed to dye particles, and a color of the dye material is changed through a reaction to a specific gas.

2. The polymer nanofiber sensor of claim 1, wherein the dye material includes lead(II) acetate whose color is changed during a reaction to hydrogen sulfide (H.sub.2S) such that lead sulfide (PbS) is formed.

3. The polymer nanofiber sensor of claim 1, wherein the dye material includes lead(II) acetate trihydrate (Pb(CH.sub.3COO).sub.2.3H.sub.2O, 75° C. of melting point) having relatively low melting point, which is selected from lead(II) acetate anhydrous (Pb(CH.sub.3COO).sub.2, 280° C. of melting point) and lead(II) acetate trihydrate.

4. The polymer nanofiber sensor of claim 1, wherein the dye material is elongated in a longitudinal direction during an electrospinning process of an electrospinning solution including the polymer and the dye material, such that the dye material is formed in the shape of a biconvex lens in which a ratio of a long axis to a short axis is more than 1.

5. The polymer nanofiber sensor of claim 1, wherein, when the dye material in the shape of a biconvex lens in which a ratio of a long axis to a short axis is more than 1, a diameter of the short axis includes a range of 10 to 500 nm and a diameter of the long axis includes a range of 100 nm to 5 μm such that the dye material having a particle shape is coupled to the polymer nanofiber.

6. The polymer nanofiber sensor of claim 1, wherein the dye material includes lead(II) acetate trihydrate, and wherein the polymer and lead(II) acetate trihydrate are melted at a high temperature of more than melting point (75° C.) of lead(II) acetate trihydrate to form an electrospinning solution, the electrospinning solution is dipped in cooling water, and the electrospinning solution performs an electrospinning process such that a dye-polymer complex nanofiber is formed in which the dye material is intensively coupled to the polymer nanofiber without desorption.

7. The polymer nanofiber sensor of claim 1, wherein the polymer nanofiber has a diameter range of 50 nm to 2 μm.

8. The polymer nanofiber sensor of claim 1, wherein the dye material has a weight rate range of 0.5 to 90 wt % with respect to polymer included in the polymer nanofiber.

9. A method of manufacturing a polymer nanofiber sensor for gas indication, the method comprising: forming an electrospinning solution in which a dye material and a polymer is blended in a solvent, the dye material and the polymer blended in the solvent is stirred at a high temperature of more than melting point to liquefy the dye material; forming crystals of the dye material liquefied in the electrospinning solution through quenching; and discharging the electrospinning solution using an electrospinning equipment onto a collector such that polymer nanofiber, in which the dye material is coupled to an inner part and a surface of the polymer nanofiber, is formed.

10. The method of claim 9, wherein, in the manufacturing of the electrospinning solution in which the dye material and the polymer is blended in the solvent, the dye material and the polymer blended in the solvent is stirred at the high temperature of more than melting point to liquefy the dye material, lead(II) acetate trihydrate functioning as the dye material and the polymer is blended in the solvent, and lead(II) acetate trihydrate is stirred at the higher temperature than the melting point of stirred lead(II) acetate trihydrate, such that the electrospinning solution is formed by liquefying lead(II) acetate trihydrate.

11. The method of claim 9, wherein the dye material includes lead(II) acetate trihydrate, and wherein, in the solidifying of the crystals of the dye material liquefied in the electrospinning solution through quenching, the electrospinning solution is rapidly quenched such that fine particles of lead acetate liquefied in a solution including the polymer are crystallized.

12. The method of claim 9, further comprising: evaluating color change when a gas is injected to the polymer nanofiber in which the dye material is coupled to the inner part and surface of the polymer nanofiber.

13. The method of claim 9, wherein the dye material coupled to the inner part and surface of the polymer nanofiber includes at least one particle having a biconvex lens shape in which a ratio of a long axis to a short axis is more than 1.

14. The method of claim 13, wherein the at least one of particle is a powder shape including a short axis diameter range of 10 to 500 nm.

15. The method of claim 9, wherein the polymer includes one selected from polymethyl methacrylate (PMMA), polyacryl copolymer, polyvinyl acetate copolymer, polymethyl alcohol (PVA), polymethyl acrylate (PMA), polyvinyl acetate (PVAc), polyperfuryl alcohol (PPFA), polystyrene (PS), polyvinylpyrrolidone (PVP), polystylene copolymer, polyethylene oxide (PEO), polyurethane, polyurethane copolymer, cellulose acetate, polypropylene oxide (PPO), polyacrylonitrile (PAN), polycarbonate (PC), polyvinyl chloride (PVC), polymer carprolactone (PCL), polyvinyl fluoride, polyaniline (PANI), styrene-acrylonitrile (SAN), polyvinyl alcohol (PVA), polycarbonate (PC), polymer(vinylidene fluoride) (PVDF), polymer(vinylidene fluoride) copolymer, polyimide, polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), cellulose, acetate butyrate, and a cellulose derivative, or a combination of at least two thereof.

16. The method of claim 9, wherein the solvent has a weight rate having a concentration range of 50 to 99 wt % with respect to the dye material.

17. The method of claim 9, wherein the solvent includes one of dimethylformamide (DMF), ethanol, acetone, dimethylacetamide (DMAc), tetrahydrofuran, toluene, dimethyl sulfoxide (DMSO), and ethylene glycol (EG) or a combination of at least two thereof.

18. The method of claim 9, wherein the dye material includes lead(II) acetate trihydrate, and wherein, in the forming of the crystals of the dye material liquefied in the electrospinning solution through quenching, the electrospinning solution including lead(II) acetate trihydrate liquefied by stirring is rapidly quenched at a temperature of less than 25° C. such that lead(II) acetate trihydrate are crystallized in the electrospinning solution.

19. The method of claim 9, wherein, in the discharging of the electrospinning solution using the electrospinning equipment to the collector, the polymer nanofiber in which the dye material is coupled to the inner part and surface of the polymer nanofiber is formed, the electrospinning solution is discharged to a current collector including nonwoven fabrics using the electrospinning equipment such that a complex nanofiber membrane including the polymer nanofiber in which the dye material is coupled to and the inner part and surface of the polymer nanofiber is formed; and the complex nanofiber membrane has a thickness range of 5 to 100 μm.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0021] The above and other objects and features will become apparent from the following description with reference to the following figures, wherein like reference numerals refer to like parts throughout the various figures unless otherwise specified, and wherein:

[0022] FIG. 1 is a block diagram of a dye/polymer complex nanofiber colorimetric sensor in which nanoparticles are uniformly coupled on an inner part and a surface of the nanofiber according to an embodiment of the present disclosure;

[0023] FIG. 2 is a block diagram of a dye/polymer complex nanofiber colorimetric sensor in which nanoparticles are uniformly coupled on an inner part and a surface of the nanofiber using an electrospinning process according to an embodiment of the present disclosure;

[0024] FIG. 3 is a flowchart of a manufacturing process of a dye/polymer complex nanofiber colorimetric sensor, in which nanoparticles are uniformly coupled on an inner part and a surface of the nanofiber according to an embodiment of the present disclosure;

[0025] FIG. 4 is a picture of a scanning electron microscope of a dye/polymer complex nanofiber colorimetric sensor synthesized through an electrospinning process according to an example 1 of the present disclosure;

[0026] FIG. 5 is a picture of a scanning electron microscope of pure lead(II) acetate trihydrate dye particles according to comparative example 1;

[0027] FIG. 6 is a picture of a scanning electron microscope of a dye/polymer complex nanofiber synthesized through an electrospinning process without high-temperature stirring and quenching according to comparative example 2;

[0028] FIG. 7 shows colorimetric variation when example 1 (7-a), comparative example 1 (7-b), and comparative example 2 were directly exposed to hydrogen sulfide gas at room temperature under a dry environment without humidity during 1 minute as concentrations of the hydrogen sulfide gas were at 5, 1, and 0 ppm, respectively.

[0029] FIG. 8 shows colorimetric variation when example 1 was exposed to hydrogen sulfide gas as an exposure time was decreased to 60, 50, 40, 30, 20, 10, and 0 seconds.

DETAILED DESCRIPTION

[0030] Embodiments of the present disclosure relates to a method of manufacturing a polymer nanofiber sensor for detecting hydrogen sulfide gas in which, after a dye is stirred at a higher temperature than the melting point to be liquefied during manufacturing an electrospinning solution, fine dye particles are uniformly dispersed in a polymer solution through a quenching process and the dye particles are coupled to an inner part and a surface of the polymer nanofiber without desorption using an electrospinning process.

[0031] As an embodiment, a dye/polymer complex colorimetric nanofiber sensor, in which lead(II) acetate trihydrate, i.e. a dye material for generating color change when being exposed to hydrogen sulfide gas, uniformly remains on an inner part and an outer part (a surface) of an one-dimensional polymer nanofiber, and a method of manufacturing the same are provided.

[0032] In a detailed embodiment, among lead(II) acetate anhydrous (Pb(CH.sub.3COO).sub.2, 280° C. of the melting point) and lead(II) acetate trihydrate (Pb(CH.sub.3COO).sub.2.3H.sub.2O, 75° C. of the melting point), when lead(II) acetate anhydrous having high melting point is used in a manufacturing process of an electrospinning solution, such a high temperature of the melting point of lead(II) acetate anhydrous may melt and decompose polymers blended therein. Accordingly, lead(II) acetate trihydrate having a relatively low melting point may be used as dye particles such that lead(II) acetate trihydrate may be stirred at a higher temperature than the melting point to be liquefied. Then, the dye particles are recrystallized through a quenching process to have fine sizes and the dye particles of tens-of-nanometer to hundreds-of-nanometer are coupled to the polymer nanofibers obtained through the electrospinning. In this process, each particle is formed in the shape of a biconvex lens shape in which a ratio of a long axis to a short axis of each particle is more than 1 such that a nanofiber colorimetric sensor membrane including the particles may be provided. Since the dye particles are strongly coupled to the inner part and the surface of each nanofiber constituting an one-dimensional porous fiber structure, an analyte gas may be diffused into a three-dimensional structure including the dye particles such that reaction sites confined to the surface are provided to the inner part, thereby significantly increasing reaction area.

[0033] In embodiments of the present disclosure, the polymer nanofiber sensor to which the dye is coupled may be massively manufactured using the electrospinning process. A polymer nanofiber sensor for detecting a gas in which, since the polymer nanofiber sensor for detecting the gas secures a surface area and porosity higher than an existing test paper for detecting hydrogen sulfide, visible color change to a specific gas having a low concentration of less than 1 ppm, which is impossible to be detected using existing colorimetric sensors, occurs, and a method of the same may be provided.

[0034] Hereinafter, in example 1 which will be described, a manufacturing process of a polymer nanofiber sensor for detecting hydrogen sulfide gas used as a specific gas is described in detail. Furthermore, in comparative example 1, dye particles bought in market was used as a material for a colorimetric sensor of hydrogen sulfide gas. In comparative example 2, a polymer nanofiber sensor for detecting hydrogen sulfide was manufactured using an electrospinning solution which did not perform high-temperature stirring and quenching. Colorimetric variation of example 1, comparative example 1, and comparative example 2 upon exposure of a small quantity of hydrogen sulfide gas were compared. Herein, examples 1 may show improved colorimetric properties in comparison to comparative example 1 and comparative example 2 since reaction sites and porosity are increased due to increase of a specific surface area.

[0035] FIG. 1 is a block diagram of a colorimetric sensor for detecting hydrogen sulfide gas, in which fine dye particles are coupled to an inner part and a surface of a polymer nanofiber. The polymer nanofiber 101 illustrated in FIG. 1 may include a diameter range of 50 nm to 10 μm. The diameter of the polymer nanofiber 101 may be adjusted by discharge speed, a diameter of a nozzle, viscosity of a spinning solution, or an applied voltage. When the diameter of the nanofiber is increased, the dye particles are formed on the inner part of the fiber instead of the surface of the fiber, such that the dye particles are not reacted to a gas, which is supposed to be detected, thereby decreasing detectability. Whereas, when the nanofiber is thin, the size of each dye particle is relatively increased such that the dye particles are not coupled to the fiber, such that the particles may be dispersed between nanofibers. Accordingly, it is effective that the diameter of the nanofiber 101 which functions as a supporter of the dye/polymer complex nanofiber may be 50 nm to 10 μm. The sensor, which is structurally stable and has the most noticeable color change to the analyte, may be advantageously manufactured using the polymer nanofiber 101 having the diameter range of 100 nm to 1000 nm.

[0036] Furthermore, the size of each dye particle 102 coupled to the polymer nanofiber 101 is an important component influencing colorimetric sensitivity. The size (one of a diameter, a length, and a thickness based on a shape of the dye particle) of the dye particle may include a range of 10 nm to 2 μm. As the size of the dye particle is decreased, the dye particles provide high surface area. However, when the size of the dye particle is much less than the diameter of the nanofiber, in the electrospinning process, the dye particles remain in the inner part of the nanofiber such that the dye particles are not reacted to the detecting gas, such that preventing the dye particles from functioning as the reaction site. In contrast with, when the dye particle is too large, in the electrospinning process, the surface area thereof is greatly decreased and the dye particles are not coupled to the polymer nanofiber such that the dye particles each of which maintains an original shape are dispersed in the fibers. When the particles are disposed in pores of the polymer nanofiber, the particles prevent diffusion of the detecting gas and prevent colorimetric reaction of the dye coupled to the nanofiber disposed in a deep-set region. Accordingly, the dye particle may include the size range of 10 nm and 2 μm.

[0037] In addition, when the ratio of the long axis to the short axis of each dye particle 102 coupled to the polymer nanofiber 101 is more than 1 to have the biconvex lens shape, a diameter of the short axis of the dye particle may include a range of 10 to 500 nm and a diameter of the long axis may include a range of 100 nm to 5 μm.

[0038] FIG. 2 is a block diagram of an electrospinning equipment used in a first embodiment of the present disclosure. Hereinafter, the electrospinning process will be described. Strong electric field is applied to a nozzle 201 disposed at the end of an injector using a high voltage application device 202 such that a solvent of the electrospinning solution discharged from the nozzle 201 is vaporized and the dye/polymer complex nanofiber is formed and collected on a collector 203. The complex fiber discharged from the nozzle is an one-dimensional nanofiber. any solvent is used to manufacture the electrospinning solution as long as the solvent dose not dissolve the dye, i.e. lead(II) acetate trihydrate. For example, the solvent may include one of dimethylformamide (DMF), ethanol, acetone, dimethylacetamide (DMAc), tetrahydrofuran, toluene, dimethyl sulfoxide (DMSO), and ethylene glycol (EG), or a combination of at least two thereof.

[0039] The dye/polymer complex colorimetric nanofiber includes polymer nanofibers 204 maintaining a fiber structure and dye particles 206 which are uniformly coupled to the polymer nanofibers 204 and are reacted to an detecting gas such that color change occurs. The polymer may include one selected from polymethyl methacrylate (PMMA), polyacryl copolymer, polyvinyl acetate copolymer, polymethyl alcohol (PVA), polymethyl acrylate (PMA), polyvinyl acetate (PVAc), polyperfuryl alcohol (PPFA), polystyrene (PS), polyvinylpyrrolidone (PVP), polystylene copolymer, polyethylene oxide (PEO), polyurethane, polyurethane copolymer, cellulose acetate, polypropylene oxide (PPO), polyacrylonitrile (PAN), polycarbonate (PC), polyvinyl chloride (PVC), polymer carprolactone (PCL), polyvinyl fluoride, polyaniline (PANI), styrene-acrylonitrile (SAN), polyvinyl alcohol (PVA), polycarbonate (PC), polymer(vinylidene fluoride) (PVDF), polymer(vinylidene fluoride) copolymer, polyimide, polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), cellulose, acetate butyrate, and a cellulose derivative, or a combination of at least two thereof. A content of the polymer to the solvent is not limited. However, in general, the solvent may be selected from a range of 5 wt % to 30 wt % with respect to the solvent for having proper viscosity to perform the electrospinning process.

[0040] The electrospinning solution injected to the nozzle includes the dye 205, which is reacted to hydrogen sulfide such that the dye 205 turns brown. In the above-described process, lead(II) acetate trihydrate having a relatively low melting point may be used as a material constituting the dye 205. Lead acetate is in an anhydrous state and a trihydrate state in nature. In the case of lead(II) acetate anhydrous, it is reported that its melting point is 280° C., and when a temperature of lead(II) acetate anhydrous is increased to liquefaction point, other polymers in the solution does not maintain original shapes or properties thereof since the other polymers are melted or to be decomposed. However, since the melting point of lead(II) acetate trihydrate is 75° C. which is lower than glass transition point of most of polymers, polymers blended in lead(II) acetate trihydrate may maintain original states thereof, such that polymers are not affected from the temperature although lead(II) acetate trihydrate is stirred at the liquefaction point thereof. Therefore, lead(II) acetate trihydrate may be selected as the material constituting the dye 205. A weight percent of the solvent of the dye 205 may include a range of 50 wt % to 99 wt % with respect to lead(II) acetate trihydrate constituting the dye/polymer nanofiber complex. A rate of the spinning solution discharged from the nozzle may be selected from a range of 0.1 μL/min to 250 μL/min based on viscosity of the spinning solution. A voltage applied to the nozzle may be selected between 5 kV to 30 kV. A distance between the nozzle and the collector may be selected from a range of 3 cm to 50 cm.

[0041] FIG. 3 is a flowchart of a manufacturing process of a colorimetric sensor for detecting hydrogen sulfide gas using a dye/polymer complex nanofiber structure in which fine dye particles formed through high-temperature stirring and quenching are uniformly coupled to an inner part and a surface of the nanofiber using electrospinning according to an embodiment of the present invention.

[0042] In operation 301, the electrospinning solution including the liquefied dye may be manufactured through stirring at a high temperature. Herein, for obtaining the fine dye particles, the dye, the polymer, and the solvent may be stirred at a higher temperature than the melting point of the dye such that the electrospinning solution may be manufactured.

[0043] In operation 302, the electrospinning solution including the dye, which is crystallized to form microcrystals, may be manufactured. For example, the electrospinning solution formed in operation 301 may perform quenching to crystallize the dye such that the dye transforms into the microcrystals.

[0044] In operation 303, the one dimensional dye/polymer complex colorimetric nanofiber may be formed using an electrospinning equipment.

[0045] In operation 304, the discharged dye/polymer complex colorimetric nanofiber having a membrane structure may be collected on a collector.

[0046] Hereinafter, the preset disclosure will be explained through detailed examples, in detail. The examples are for illustrative purposes only, and the present disclosure is not limited thereto.

Example 1: Dye/Polymer Complex Nanofiber Synthesized Through Electrospinning of Spinning Solution Obtained by High-Temperature Stirring and Quenching of Lead(II) Acetate Trihydrate Lead(II)

[0047] For manufacture of the electrospinning solution, 0.45 g of lead(II) acetate trihydrate, 0.25 g polyacrylonitrile (PAN) having 150,000 g of molecular weight were blended into 3 ml of dimethylformamide (DMF). In order that a grain size of each dye particle was decreased to sub-μm, the dye was stirred at 90° C. i.e. more than melting point of the dye during 24 hours. A beaker, in which the electrospinning solution heated at 90° C. was contained, was rapidly dipped into a cooling water such that the quenching was performed. Therefore, the fine dye particles were synthesized while crystal grain growth of lead(II) acetate trihydrate was controlled.

[0048] The spinning solution was connected to a nozzle. For performance of the electrospinning, 17 kV of a voltage was applied to the nozzle and a distance between the nozzle and the collector was 15 cm. In addition, a discharge rate from the nozzle was 0.3 ml/min.

[0049] FIG. 4 is a picture of a scanning electron microscope of the dye/polymer complex nanofiber synthesized through the electrospinning process. In the electrospinning process, the polymer was elongated in a longitudinal direction such that the polymer nanofiber had the diameter of about 500 nm, while the fine dye particles remaining on the polymer and were discontinuously formed in the shape of a biconvex lens in which a ratio of a long axis to a short axis of each particle was more than 1.

Comparative Example 1. Pure Lead(II) Acetate Trihydrate Dye Particles

[0050] In comparative example 1, the pure dye particles bought on the market without the electrospinning process, unlike example 1, were used.

[0051] FIG. 5 is a picture of a scanning electron microscope of the pure dye particles without the electrospinning process. It was shown that a size of each pure dye particle was more than 100 μm.

Comparative Example 2. Dye/Polymer Complex Nanofiber Synthesized by Electrospinning without High-Temperature Stirring and Quenching

[0052] For manufacturing the electrospinning solution to be injected to the nozzle, after 0.45 g of lead(II) acetate trihydrate which was bought in market, 0.25 g polyacrylonitrile (PAN) having 150,000 g of molecular weight were blended into 3 ml of dimethylformamide (DMF), the electrospinning solution was stirred at room temperature during 24 hours. The electrospinning solution was connected to the nozzle.

[0053] For performing the electrospinning process, a voltage of 17 kV was applied to the nozzle and a distance between the nozzle and the collector was 15 cm. In addition, a discharge rate from the nozzle was 0.3 ml/min.

[0054] FIG. 6 is a picture of a scanning electron microscope of the dye/polymer complex nanofiber formed by the electrospinning process. It was shown that a diameter distribution of the formed polymer nanofiber was about 1 μm. However, the nanofiber having the remaining dye particles could not be seen. Some bulk dye disposed in the nanofibers could be seen. This is because a great quantity of lead(II) acetate trihydrate of more than 1 μm, which was grinded by only stirring without high-temperature stirring and quenching, was hardly coupled to the surface and the inner part of the nanofiber. Accordingly, after the dye was liquefied through high-temperature stirring, crystal growth was controlled through quenching such that proper size combination of the dye particles was obtained. Therefore, the nanofiber coupled to the dye particles might be achieved.

[0055] Through below experimental example 1, when the dye/polymer nanofiber synthesized by discharging the electrospinning solution, which performed high-temperature stirring and quenching, was compared to comparative examples, it was shown that the example according to present disclosure had high detecting properties and therefore color of the dye/polymer complex nanofiber was changed although the dye/polymer complex nanofiber was exposed to a small amount of hydrogen sulfide gas.

Experimental Example 1. Colorimetric Evaluation for Detecting Hydrogen Sulfide Gas Using Dye/Polymer Complex Nanofiber Synthesized by Electrospinning Solution Performing High-Temperature Stirring and Quenching, Pure Lead(II) Acetate Trihydrate Dye Particles, and Dye/Polymer Complex Nanofiber Synthesized by Spinning without Performance High-Temperature Stirring and Quenching

[0056] For evaluating colorimetric properties to hydrogen sulfide gas, materials obtained through example 1, comparative example 1, and comparative example 2 were directly exposed to hydrogen sulfide (H.sub.2S) gas at normal atmospheric environment (20° C. and relative humidity of 40%) during 1 minute at a tube connected to a gas outlet as concentrations of the hydrogen sulfide gas were at 5, 1, and 0 ppm, and then the colorimetric properties were evaluated based on concentration change of the gas.

[0057] FIG. 7 shows colorimetric variation when example 1 (7-a), comparative example 1 (7-b), and comparative example 2 were directly exposed to hydrogen sulfide gas at atmospheric environment (20° C. and relative humidity of 40%) during 1 minute as concentrations of the hydrogen sulfide gas were at 5, 1, and 0 ppm.

[0058] As illustrated in FIG. 7, the dye/polymer complex colorimetric nanofiber (7-a), which performed electrospinning after high-temperature stirring and quenching, visually detected distinct color change at 1 ppm. On the contrary, it was shown that the pure lead(II) acetate trihydrate dye particles (7-b) did not display color change at 1 ppm. It was shown that the nanofiber including the dye particles (7-c) without high-temperature stirring and quenching did not display color change at 1 ppm. The dye/polymer complex colorimetric nanofiber (7-a) synthesized by electrospinning solution including the fine dye particles formed through high-temperature stirring and quenching, displayed distinct color change when being exposed to the hydrogen sulfide gas having a low concentration, in comparison with the dye particles (7-b) without the electrospinning process and the dye/polymer complex colorimetric nanofiber (7-c) without high-temperature stirring and quenching.

[0059] FIG. 8 shows colorimetric variation when example 1 was exposed to hydrogen sulfide gas as an exposure time was decreased to 60, 50, 40, 30, 20, 10, and 0 seconds. As illustrated in FIG. 8, it was shown that distinct brown color at 1 ppm became pale as the exposure time was shortened. Color change of the nanofiber membrane exposed to sulfur gas was visually recognized up to 30 seconds. This was because lead(II) acetate trihydrate having a size of tens-of-nanometer to hundreds-of-nanometer were coupled to the surface and the inner part of the polymer nanofiber having a diameter of hundreds-of-nanometer such that gas reaction of hydrogen sulfide gas was generated at a large area. The distinct colorimetric properties was shown at a hydrogen sulfide concentration of less than 1 ppm such that hydrogen sulfide functioning as noxious environment gas and hydrogen sulfide discharged from respiration, i.e. a biomarker gas of halitosis were detected through the colorimetric sensor according to the embodiments.

[0060] As is apparent from the above description, according to the present invention, after lead(II) acetate trihydrate is stirred at a high temperature to be liquefied and the fine dye particles in a liquid state is uniformly dispersed in the solution, quenching is performed such that the lead(II) acetate trihydrate dye particles having a size of tens-of-nanometer and hundreds-of-nanometer, in particularly, having a size range of 20 to 500 nm are obtained. The dispersed solution performs the electrospinning process such that the complex nanofiber detecting material, in which the fine dye particles uniformly remains in the inner and outer parts of the one-dimensional nanofiber, is synthesized. Thereby, the polymer nanofiber sensor for detecting hydrogen sulfide gas, which is coupled to the fine lead(II) acetate particles able to selectively react with the small amount of hydrogen sulfide, may be provided.

[0061] The dye/polymer complex nanofiber has the surface area and porosity which are higher than those of the dye material of the existing test paper for detecting hydrogen sulfide. Therefore, although the dye/polymer complex nanofiber is exposed to hydrogen sulfide having a concentration of less than 1 ppm, color change is visible within tens-of-second such that the dye/polymer complex nanofiber may be used as the colorimetric sensor capable of diagnosing halitosis and monitoring noxious hydrogen sulfide gas with a high sensitivity and at high speed.

[0062] While the inventive concept has been described with reference to exemplary embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the inventive concept. Therefore, it should be understood that the above embodiments are not limiting, but illustrative.