Photoelectric dual-mode ethanolamine gas sensor material and preparation method thereof

Abstract

The invention relates to a photoelectric dual-mode ethanolamine gas sensor material and a preparation method thereof. The photoelectric dual-mode ethanolamine gas sensor material comprises the following components in percentage by mass: 5-25% of a fiber-based high-molecular compound; 5%-20% of a nonionic high-molecular compound; 1%-12% of an inorganic salt compound; 0.5%-5% of an ionic liquid; the preparation method is used for preparing the material disclosed by the invention. According to the photoelectric dual-mode ethanolamine gas sensor material and the preparation method thereof, the reliability and the practicability are good, overflow of trace gas can be observed by naked eyes, the experimental design requirements of greenness, low cost, fast response, easiness in operation and qualitative and quantitative properties are met, and a more reliable technical scheme is provided for industrial field trace gas leakage monitoring.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sensor materials, in particular to a photoelectric dual-mode ethanolamine gas sensor material and a preparation method thereof. BACKGROUND

[0002] Ethanolamine is an important chemical raw material but has strong corrosive and toxic properties. Its gas research is of great significance to biological medicine - rapid detection and toxicity mechanism research are needed to protect occupational health and public health. In terms of national development, green control technology meets the "double carbon" requirement, and independent innovation in detection and protection technology can enhance the core competitiveness of the electronic information industry and support industrial upgrading. Therefore, the production and use environment needs to be monitored in real time.

[0003] Existing ethanolamine detection technologies mainly include gas chromatography (which requires large equipment and is not portable), spectroscopy (which has low sensitivity and is easily disturbed), and metal oxide sensors (which have high working temperatures and poor selectivity). In recent years, optical sensors and capacitive sensors have become research hotspots, but they have the following defects: 1. Optical sensors (main disadvantage: poor precision): mostly single optical materials, weak mechanical properties, easily affected by environmental factors (such as humidity), and difficult to achieve accurate quantification; 2. Capacitive sensors (main disadvantage: unable to achieve portable detection): mostly thin film structures, small specific surface area, slow response speed, and lack of intuitive visual qualitative. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a photoelectric dual-mode ethanolamine gas sensor material and a preparation method thereof, which has good reliability and practicability, can visually observe the overflow of trace gas, meets the experimental design requirements of green, low cost, fast response, easy operation, and qualitative and quantitative, and provides a more reliable technical solution for industrial site trace gas leakage monitoring.

[0005] The present application provides a photoelectric dual-mode ethanolamine gas sensor material, which comprises, by mass percentage:

[0006] 5% to 25% of a fiber base polymer compound;

[0007] 5% to 20% of a non-ionic polymer compound;

[0008] 1% to 12% of an inorganic salt compound;

[0009] 0.5% to 5% of an ionic liquid;

[0010] 55% to 75% of a polar solvent.

[0011] In an embodiment, the fiber base polymer compound comprises one or more of polymethyl acrylonitrile, polyethylene terephthalate, polyamide, polyimide, polyacrylonitrile, and polyvinylidene fluoride.

[0012] In one embodiment, the nonionic polymeric compound includes one or more of polyvinyl alcohol, polyethylene glycol, and polyvinylpyrrolidone.

[0013] In one embodiment, the inorganic salt compound includes one or more of ferrous chloride dihydrate, zinc chloride dihydrate, copper chloride dihydrate, cobalt chloride hexahydrate, and manganese chloride tetrahydrate.

[0014] In one embodiment, the ionic liquid comprises one or more of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-butyl-3-methylimidazolium tetrafluoroborate.

[0015] In one embodiment, the polar solvent includes one or more of N,N-dimethylformamide or acetone.

[0016] This invention also provides a method for preparing a photoelectric dual-mode ethanolamine gas sensor material, used for preparing the photoelectric dual-mode ethanolamine gas sensor material described in any one of the above-mentioned methods, comprising the following steps:

[0017] Add 1% to 12% of the inorganic salt compound to 55% to 75% of the polar solvent and stir thoroughly until completely dissolved to form a mixed solution.

[0018] Add 5%–25% of the fiber-based polymer compound and 5%–20% of the nonionic polymer compound to the mixed solution and stir thoroughly until completely dissolved;

[0019] Electrospinning was performed to obtain a fiber membrane, and then 0.5% to 5% ionic liquid was injected into the fiber membrane to obtain a photoelectric dual-mode ethanolamine gas sensor material.

[0020] The photoelectric dual-mode ethanolamine gas sensor material and preparation method provided by this invention have good reliability and practicality. The leakage of trace amounts of gas can be observed with the naked eye. It meets the experimental design requirements of green, low cost, fast response, easy operation and qualitative and quantitative analysis, and provides a more reliable technical solution for monitoring trace gas leaks in industrial sites. Attached Figure Description

[0021] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1The application provides a preparation method of a photoelectric bimodal ethanol amine gas sensor material.

[0023] Figure 2 The application provides an optical micrograph of a fiber membrane obtained by the preparation method of the photoelectric bimodal ethanol amine gas sensor material.

[0024] Figure 3 The application provides a scanning electron microscope (SEM) image of the fiber membrane obtained by the preparation method of the photoelectric bimodal ethanol amine gas sensor material.

[0025] Figure 4 The application provides an optical micrograph of the fiber membrane filled with the ionic liquid on the interdigital electrode.

[0026] Figure 5 The application provides a scanning electron microscope (SEM) image of the photoelectric bimodal ethanol amine gas sensor material obtained by the preparation method.

[0027] Figure 6 The application provides a hue shift diagram of a sample obtained by the photoelectric bimodal ethanol amine gas sensor material in the application example four after detecting low-concentration ethanol amine gas.

[0028] Figure 7 The application provides a diffuse reflectance absorption spectrum diagram of the photoelectric bimodal ethanol amine gas sensor material obtained by the application example four after detecting low-concentration ethanol amine gas.

[0029] Figure 8 The application provides a dependence curve of the photoelectric bimodal ethanol amine gas sensor material obtained by the application example four and wavelength after detecting low-concentration ethanol amine gas.

[0030] Figure 9 The application provides a hue shift diagram of a sample obtained by the photoelectric bimodal ethanol amine gas sensor material in the application example five after detecting high-concentration ethanol amine gas.

[0031] Figure 10 The application provides a diffuse reflectance absorption spectrum diagram of the photoelectric bimodal ethanol amine gas sensor material obtained by the application example five after detecting high-concentration ethanol amine gas.

[0032] Figure 11 The application provides a dependence curve of the photoelectric bimodal ethanol amine gas sensor material obtained by the application example five and light intensity after detecting high-concentration ethanol amine gas.

[0033] Figure 12 The application provides an electrical signal response curve diagram of the photoelectric bimodal ethanol amine gas sensor material obtained by the application example six.

[0034] Figure 13The dependence diagram of the ethanol amine gas concentration and the electric signal change amount of the photoelectric dual-mode ethanol amine gas sensor material obtained in Embodiment Six of the present application is shown in Figure 6. DETAILED DESCRIPTION

[0035] The specific embodiments of the present application will be described in detail hereinafter with reference to the drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the description of the present application, all the other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present application.

[0036] In the description of the present application, unless explicitly specified and limited, the terms "arrange", "mount", "connect" and the like shall be understood in a broad sense, for example, can be fixedly connected, or detachably connected, or integrally connected; can be mechanically connected, or electrically connected; can be directly connected, or indirectly connected through an intermediate medium. The specific meanings of the above terms can be understood according to the specific circumstances by those of ordinary skill in the art.

[0037] The terms "upper", "lower", "left", "right", "front", "back", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship when the product of the present application is usually placed, and are only for the convenience of description and simplification of the description, and do not indicate or imply that the indicated device or element must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application.

[0038] The terms "first", "second", "third" and the like are only for distinguishing similar attributes of elements, and do not indicate or imply relative importance or a particular order.

[0039] The terms "include", "contain" or any other variants thereof are intended to cover non-exclusive inclusion, in addition to including the listed elements, other elements not explicitly listed can also be included.

[0040] Embodiment One

[0041] Please refer to Figures 1-4 The photoelectric dual-mode ethanol amine gas sensor material provided by the present application is as follows in terms of mass percentage:

[0042] 14% PAN (polyacrylonitrile);

[0043] 10% PVP (polyvinylpyrrolidone);

[0044] 8% CuCl2·2H2O (copper chloride dihydrate);

[0045] 2% [EMIM][TFSI] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide);

[0046] 66% mL DMF (N,N-dimethylformamide).

[0047] Example Two

[0048] The application provides a preparation method of the photoelectric bimodal ethanol amine gas sensor material, and the preparation method of the material in Example One comprises the following steps: 0.2g of CuCl2·2H2O is placed in a 10mL sample bottle, 1.65mL of DMF is added, heating is performed on a hot stage at 30-80℃, complete dissolution is realized, then 0.35g of PAN and 0.25g of PVP are added, sufficient stirring is performed, a period of time is kept still to remove bubbles, a yellow-green optical spinning stock solution is obtained, and electrospinning is performed to obtain a fiber membrane; the fiber membrane is transferred to an interdigital electrode, and then 0.05g of [EMIM][TFSI] ionic liquid is filled into the fiber membrane.

[0049] Example Three

[0050] As shown in Figure 5 , the photoelectric bimodal ethanol amine gas sensor material provided by the application comprises the following components in percentage by mass:

[0051] 8% CuCl2·2H2O;

[0052] 66% DMF;

[0053] 24% PVDF;

[0054] 2% [EMIM][TFSI].

[0055] 0.2g of CuCl2·2H2O is placed in a 10mL sample bottle, 1.65mL of DMF is added, heating is performed on a hot stage at 30-80℃, complete dissolution is realized, then 0.6g of PVDF is added, sufficient stirring is performed, a period of time is kept still to remove bubbles, a yellow-green optical spinning stock solution is obtained, and electrospinning is performed to obtain a fiber membrane.

[0056] As shown in Figure 5 , it is a scanning electron microscope image of the fiber membrane in the photoelectric bimodal ethanol amine gas sensor provided by Example Three of the application, the obtained fiber diameter is uniform, the surface is smooth, and the fiber membrane has high porosity, which is beneficial to binding ionic liquid.

[0057] Example Four

[0058] As shown in Figures 6-8 , the application provides an application of the photoelectric bimodal ethanol amine gas sensor, which can be an application in optical signal detection, and the specific steps are as follows:

[0059] The sensor was placed in a sealed chamber measuring 30×60×15 cm, and different volumes of ethanolamine liquid were dropped onto a heated substrate. After heating to 60-80°C, the ethanolamine liquid gradually evaporated, forming gaseous molecules that filled the entire chamber in approximately 3-5 minutes. At this point, the sensor exhibited a noticeable color change; as the concentration of ethanolamine gas varied from 0-10 ppm, the sensor gradually shifted from an initial yellowish-green to a light blue, as shown in the image. Figure 6 As shown. Its absorbance change can be quantitatively characterized by diffuse reflectance absorption spectroscopy, such as... Figure 7 As shown, the response exhibits good concentration dependence—the higher the concentration, the more pronounced the blue shift, and the closer the color becomes to a lighter blue. The gas concentration shows a good linear relationship with the center wavelength, with a good fit R0. 2 = 0.994, such as Figure 8 As shown in the figure, this embodiment demonstrates that the leakage of trace gases can be observed with the naked eye through optical signals, realizing a green, low-cost, and easy-to-operate visual monitoring technology for trace gases, which has potential applications in practical applications.

[0060] Example 5

[0061] This embodiment provides an application of a photoelectric dual-mode ethanolamine gas sensor, specifically in optical signal detection. The specific steps are as follows:

[0062] The sensor was placed in a sealed chamber measuring 30×60×15 cm, and different volumes of ethanolamine liquid were dropped onto a heating substrate. After heating to 60-80°C, the ethanolamine liquid gradually evaporated, forming gaseous molecules that filled the entire chamber in approximately 3-5 minutes. As the concentration of ethanolamine gas varied from 10 to 100 ppm, the sensor gradually changed from light blue to dark blue. Figure 9 As shown. Its absorbance change can be quantitatively characterized by diffuse reflectance absorption spectroscopy, such as... Figure 10 As shown, color depth is positively correlated with gas concentration—the higher the concentration, the deeper the color and the greater the light intensity. Gas concentration and light intensity exhibit a good linear relationship, with a goodness of fit R0. 2 = 0.995, such as Figure 11 As shown in the figure, this embodiment demonstrates that gas overflow can be observed with the naked eye through optical signals, realizing a green, low-cost, and easy-to-operate gas visualization monitoring technology, which has potential applications in practical applications.

[0063] Example 6

[0064] This embodiment provides an application of a photoelectric dual-mode ethanolamine gas sensor, which can be used in electrical signal detection. The specific steps are as follows:

[0065] The sensor is loaded on the surface of a 10x10 mm ITO electrode to form a capacitive gas sensitive sensor. The sensor is connected to a Tonghui TH2827A Precision LCR Meter table through a wire, and the test parameters are set to 1~2 V alternating voltage, 1 kHz operating frequency, and the capacitive signal is collected in real time. In a sealed chamber, the sensor adsorbs and captures gas molecules, changes the viscosity of the ionic liquid, and makes the capacitance value change instantaneously, with a response time of about 1.5 s, as shown in Figure 12 The gas concentration and the change amount of the electric signal have a good linear relationship, and the fitting coefficient R 2 = 0.995, as shown in Figure 13 The sensor electric signal detection limit is as low as 2 ppm, which is consistent with the optical signal detection limit, achieving the goal of high sensitivity and complementary micro gas detection of photoelectric dual-mode cooperation, realizing the dual advantages of "visual observation (optical signal) + precise quantification (electric signal)", retaining the intuitive nature of the naked eye, and providing more accurate numerical reference through the electric signal, further enhancing the reliability and practicality of the sensor, meeting the experimental design requirements of green, low cost, easy operation, qualitative and quantitative, and providing a more reliable technical solution for industrial site micro gas leakage monitoring.

[0066] From the above description, it can be known that the photoelectric dual-mode ethanolamine gas sensor material and preparation method provided by the present application have good reliability and practicality, can observe the overflow of micro gas with the naked eye, meet the experimental design requirements of green, low cost, fast response, easy operation and qualitative and quantitative, and provide a more reliable technical solution for industrial site micro gas leakage monitoring.

[0067] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the appended claims.

Claims

1. A photoelectric dual-mode ethanolamine gas sensor material, characterized in that, Including by weight percentage: 5%–25% fiber-based polymer compounds; 5%–20% nonionic polymers; 1%–12% inorganic salt compounds; 0.5%–5% ionic liquid; 55%–75% polar solvent.

2. The photoelectric dual-mode ethanolamine gas sensor material as described in claim 1, characterized in that, The fiber-based polymer compound includes one or more of polymethacrylonitrile, polyethylene terephthalate, polyamide, polyimide, polyacrylonitrile, and polyvinylidene fluoride.

3. The photoelectric dual-mode ethanolamine gas sensor material as described in claim 1, characterized in that, The nonionic polymeric compound includes one or more of polyvinyl alcohol, polyethylene glycol, and polyvinylpyrrolidone.

4. The photoelectric dual-mode ethanolamine gas sensor material as described in claim 1, characterized in that, The inorganic salt compound includes one or more of ferrous chloride dihydrate, zinc chloride dihydrate, copper chloride dihydrate, cobalt chloride hexahydrate, and manganese chloride tetrahydrate.

5. The photoelectric dual-mode ethanolamine gas sensor material as described in claim 1, characterized in that, The ionic liquid includes one or more of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imine, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-butyl-3-methylimidazolium tetrafluoroborate.

6. The photoelectric dual-mode ethanolamine gas sensor material as described in claim 1, characterized in that, The polar solvent includes one or more of N,N-dimethylformamide or acetone.

7. A method for preparing a photoelectric dual-mode ethanolamine gas sensor material, characterized in that, The preparation of the photoelectric dual-mode ethanolamine gas sensor material according to any one of claims 1 to 6 comprises the following steps: Add 1% to 12% of the inorganic salt compound to 55% to 75% of the polar solvent and stir thoroughly until completely dissolved to form a mixed solution. Add 5%–25% of the fiber-based polymer compound and 5%–20% of the nonionic polymer compound to the mixed solution and stir thoroughly until completely dissolved; Electrospinning was performed to obtain a fiber membrane, and then 0.5% to 5% ionic liquid was injected into the fiber membrane to obtain a photoelectric dual-mode ethanolamine gas sensor material.

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