CN113683855A - Gas-sensitive gel and preparation method and application thereof - Google Patents
Gas-sensitive gel and preparation method and application thereof Download PDFInfo
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- 238000001879 gelation Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 229940072056 alginate Drugs 0.000 claims abstract description 13
- 229920000615 alginic acid Polymers 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 40
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
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- -1 N, N' -methylene acrylamide Chemical compound 0.000 claims description 4
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 118
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 28
- 230000035945 sensitivity Effects 0.000 abstract description 18
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 abstract description 13
- 229920002401 polyacrylamide Polymers 0.000 abstract description 8
- 239000000499 gel Substances 0.000 description 70
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 37
- 230000004044 response Effects 0.000 description 27
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 12
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
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- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical group [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 6
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4162—Systems investigating the composition of gases, by the influence exerted on ionic conductivity in a liquid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a gas-sensitive gel and a preparation method and application thereof, wherein a cross-linked network structure is formed by two polymers, namely polyacrylamide and alginate, and the network structure also contains a certain amount of solvent and metal salt, so that the gas-sensitive gel has good tensile property and transparency, and has nitrogen dioxide sensitivity and good selectivity.
Description
Technical Field
The invention relates to the technical field of gas sensors, in particular to a gas-sensitive gel and a preparation method and application thereof.
Background
The development of a high-sensitivity gas sensor has important significance for environmental monitoring, human health, military safety and danger early warning. For exampleNO concentrations on the order of parts per million (ppm)2It will cause damage to the respiratory tract of the person and even suffocation and death due to long-term inhalation. To date, many sensing materials have been developed to produce gas sensors with high sensitivity and low cost, such as oxide semiconductors, carbon materials, and two-dimensional materials such as molybdenum disulfide. However, since most conventional sensing materials are rigid and lack deformability, it is difficult to meet the increasing demands of current flexible electronics and wearable devices. Some researchers have integrated rigid sensing materials with flexible substrates (e.g., PDMS and PI) that can subject the sensor to moderate deformations such as tensile, bending and torsional deformations, but the gas sensors obtained by this method are limited to substrates, which typically do not have a tensile range exceeding 100%. Meanwhile, if the sensor is to be applied to a wearable electronic device or an electronic skin, the appearance characteristics of the sensor also need to be optimized, such as portability and transparency.
Currently, many gas sensors respond to a plurality of gases due to the adsorption mechanism, are difficult to specifically sense a certain gas, are particularly easily interfered by the ambient humidity, and have poor selectivity. In addition, most of the gas sensors available for commercial use at present are based on oxide semiconductors, and such gas sensors generally require a high-temperature environment (> 150 ℃) to promote the sensing process during operation, so that an additional heating part needs to be manufactured, which increases the complexity and cost of device manufacturing and is not beneficial to reducing power consumption.
Chinese patent CN109187665A discloses a non-hydrolytic sol-gel based WO3NO of porous film2The gas sensor and the preparation method thereof are characterized in that nanogel particles are coated on an electrode element to prepare the gas sensor, the concentration of nitrogen dioxide can be detected, but the gas sensor has slow response and recovery to the nitrogen dioxide, the response time and the recovery time are about 14min in a 2ppm nitrogen dioxide atmosphere, the detection to the nitrogen dioxide can be realized only at a working temperature of 100 ℃, and the detection at room temperature cannot be realized.
Disclosure of Invention
The invention aims to solve the technical problems of the existing nitrogen dioxide gas sensor that the detection can not be carried out at room temperature, the response time is long and the recovery is slow, and provides a gas-sensitive gel which has high transparency and good stretchability, is used for preparing the nitrogen dioxide gas sensor, has the characteristics of high sensitivity, short response time and fast recovery, has a wide detection temperature range and can be used for detection at room temperature.
It is a further object of the present invention to provide a method for preparing a gas-sensitive gel.
It is another object of the present invention to provide the use of a gas-sensitive gel.
It is another object of the present invention to provide a NO2A gas sensor.
It is another object of the present invention to provide a NO2Use of a gas sensor.
The above purpose of the invention is realized by the following technical scheme:
the gas-sensitive gel comprises a polymer network, a solvent in the polymer network and a metal salt, wherein the polymer network is a polyacrylamide-alginate cross-linked network, the metal salt is a divalent and/or trivalent metal salt, and the concentration of the metal salt is 0.5-2 mol/L.
The gas-sensitive gel provided by the invention is used for preparing a nitrogen dioxide gas sensor, because the gas-sensitive gel is connected with a power supply and an electrode, the gas-sensitive gel can provide electrolyte, ions in the gel can participate in electric conduction, and the nitrogen dioxide gas can generate redox reaction on the electrode, and when in reaction, the metal of the anode loses electrons and is oxidized into metal ions and enters the gel; at the cathode, the nitrogen dioxide molecules get electrons and are reduced to nitric oxide, and the reaction promotes the flow of charges in the loop, resulting in an increase in current, so that a response to the nitrogen dioxide gas can be achieved at room temperature. Sodium alginate reacts with divalent and/or trivalent metal ions to form a cross-linked network structure, if the concentration of the metal salt is too low, the sodium alginate is difficult to form a network sufficiently, and the conductivity of the gel is poor and the noise is large. If the concentration of the metal salt is too high, the network formed by the sodium alginate is too compact, so that the strength of the gel is too high, the deformability is poor, and the stretching length is reduced, therefore, the metal salt ions with proper concentration can form a cross-linked network to form the gas-sensitive gel, and simultaneously, the gas-sensitive gel has higher conductivity and deformability, and the further prepared gas sensor has the characteristics of high sensitivity, short response time and quick recovery.
Preferably, the metal salt is one or more of calcium chloride, magnesium chloride, aluminum chloride and ferric chloride.
Preferably, the solvent is water and/or an alcohol solvent.
The preparation method for protecting the gas-sensitive gel comprises the following steps:
uniformly mixing acrylamide, alginate, a solvent, a crosslinking agent, an accelerant and an initiator at room temperature, pouring the obtained solution into a mold, heating to 50-90 ℃, preserving heat for 1-3 hours, cooling to obtain a gel precursor, soaking the gel precursor in an electrolyte for 1-5 hours to obtain the gas-sensitive gel, wherein the mass ratio of the acrylamide to the alginate to the solvent to the crosslinking agent to the accelerant to the initiator is 1: 0.1-0.2: 6-7: 0.0004 to 0.0006: 0.002 to 0.003: 0.005-0.008.
Preferably, the mass ratio of the acrylamide to the alginate to the solvent to the cross-linking agent to the promoter to the initiator is 1: 0.1-0.15: 6.5-7: 0.00045-0.0005: 0.0025 to 0.003: 0.005-0.006.
Preferably, the method further comprises soaking the gas-sensitive gel in an alcohol organic solvent for 10-120 min.
Preferably, the alcohol organic solvent is glycerol.
Preferably, the cross-linking agent is N, N' -methylene acrylamide and/or ethylene glycol dimethacrylate.
Preferably, the initiator is ammonium persulfate and/or potassium persulfate.
The invention protects the gas-sensitive gel in the preparation of NO2Use in a gas sensor.
NO (nitric oxide)2A gas sensor comprising a gas-sensitive gel and electrodes at either end of the gel.
Preferably, the anode of the electrode is a copper-tin alloy wire, the cathode is a silver wire or both the anode and the cathode are silver.
The conventional gas sensor realizes sensing by means of the electrical property change of a gas sensitive material in the atmosphere of gas to be detected, if gas sensors with different sensitivities are obtained, the gas sensitive material needs to be changed, a process matched with the used gas sensitive material needs to be developed, the research and development cost is high, and the process is complex. The gas-sensitive gel shows different electrode potentials due to different interaction between different electrodes and different gas-sensitive gels, so that the interaction between the electrodes and the gels can be enhanced by selecting a proper combination of the electrodes and the gas-sensitive gels under a certain external voltage, so that the generated redox reaction is more obvious and rapid, and a gas sensor with high sensitivity is obtained.
The present invention protects the above NO2The application of the gas sensor in preparing wearable electronic devices.
Compared with the prior art, the invention has the beneficial effects that:
the gas-sensitive gel has the advantages of good tensile property and transparency, and good selectivity, and can realize the response to the nitrogen dioxide gas at room temperature by using the gas-sensitive gel and a proper electrode material to prepare the nitrogen dioxide gas sensor, and the gas-sensitive gel has high sensitivity, short response time and quick recovery.
Drawings
Fig. 1 is a schematic structural view of a gas sensor according to embodiment 1 of the present invention.
FIG. 2 is a schematic diagram of the internal network structure of the gas-sensitive gel in example 1 of the present invention.
FIG. 3 is a flow chart showing the production of a gas sensor according to example 1 of the present invention.
FIG. 4 is a graph showing the transmittance of the gas-sensitive gel obtained in example 1 of the present invention in the visible light range.
FIG. 5a is a photograph of a gas-sensitive gel obtained in example 1 of the present invention in a bent and deformed state; FIG. 5b is a photograph of a gas-sensitive gel obtained in example 1 of the present invention in a twisted deformed state; FIG. 5c is a photograph of the gas-sensitive gel obtained in example 1 of the present invention in a state of being deformed by stretching.
FIG. 6a is a graph showing the results of different concentrations of NO in the case of silver on both the anode and the cathode of the gas sensor in accordance with example 1 of the present invention2The sensitivity performance test result of (2); FIG. 6b is a graph showing the comparison of NO in the case where silver is used as both the anode and the cathode in the gas sensor of example 1 of the present invention2And (5) sensitivity fitting results.
FIG. 7a is a diagram of the anode of the gas sensor of example 1 of the present invention for NO in the case where the anode is made of Cu-Sn alloy and the cathode is made of Ag2The sensitivity performance test result of (2); FIG. 7b is a graph showing the comparison of NO in the case where the anode of the gas sensor of example 1 is made of Cu-Sn alloy and the cathode of the gas sensor is made of Ag2A sensitivity fitting result; FIG. 7c is a graph showing the comparison of the tensile strain at 50% to NO for a gas sensor in accordance with example 1 of the present invention with a Cu-Sn alloy anode and a Ag cathode2The sensitivity performance test result of (2); FIG. 7d is a graph showing the relationship between the anode of the gas sensor of example 1 and the anode of the gas sensor of the present invention, which is made of Cu-Sn alloy, and the cathode of the gas sensor is made of Ag, under a bending strain of 45 DEG for NO2The result of the sensitive performance test.
Fig. 8 shows the results of the selectivity test of the gas sensor of example 2 of the present invention in the case where the anode is a copper-tin alloy and the cathode is silver.
FIG. 9a is a diagram of a gas sensor of example 2 of the present invention for NO with the anode and cathode shielded separately2The sensitivity performance test result of (2); fig. 9b is a schematic diagram of a gas sensor sensing mechanism in embodiment 2 of the present invention.
FIG. 10a is a photograph showing the change of the morphology of the gel with time before and after immersion in glycerol according to example 3 of the present invention; FIG. 10b is a graph of the percent weight loss of the gel as a function of time before and after soaking in glycerol according to example 3 of the present invention; FIG. 10c is the results of the resistance of the gel as a function of time before and after immersion in glycerol of example 3 in accordance with the present invention; FIG. 10d is a graph showing the results of the freezing point test of the gel before and after immersion in glycerol according to example 3 of the present invention.
FIG. 11 shows the measured NO ratio of the gas sensor in example 3 of the present invention with Cu-Sn alloy as the anode, Ag as the cathode and glycerin gel-soaked2The result of the sensitive performance test.
Fig. 12 shows the result of the response time test of the gas sensor of example 1 of the present invention in the case where the anode is a copper-tin alloy and the cathode is silver.
Fig. 13 shows the results of the recovery time test of the gas sensor of example 2 of the present invention with the anode made of copper-tin alloy and the cathode made of silver.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A gas-sensitive gel (or referred to as polyacrylamide/calcium alginate hydrogel) comprises a polymer network, a solvent in the polymer network and calcium chloride, wherein the polymer network is a polyacrylamide-alginate cross-linked network, and the concentration of the calcium chloride is 0.5 mol/L.
The preparation method of the gas-sensitive gel comprises the following steps:
s1, adding deionized water into a beaker, adding acrylamide and sodium alginate under the state of magnetic stirring (500rpm), then respectively adding methylene bisacrylamide, tetramethylethylenediamine and ammonium persulfate, stirring for 10min to obtain a precursor solution, pouring the obtained precursor solution into a plastic mould, sealing a preservative film, preserving heat for 2h at the temperature of 65 ℃, and naturally cooling to obtain a gel precursor; wherein the mass ratio of acrylamide, sodium alginate, deionized water, N' -methylene bisacrylamide, tetramethylethylenediamine and ammonium persulfate is 1: 0.125: 6.75: 0.0005: 0.0025: 0.006;
s2, cutting the gel precursor obtained in the step S1 into strips (30mm multiplied by 8mm), soaking in 1mol/L calcium chloride solution for 3 hours to obtain the gas-sensitive gel, wherein the preparation steps are shown in FIG. 3. The gas-sensitive gel thus prepared is shown in fig. 2 and comprises a polyacrylamide-alginate crosslinked network, a solvent dissolved in the polypropylene network, and an electrolyte dissolved in the gas-sensitive gel. The polyacrylamide network is formed by polymerizing acrylamide monomers, and the alginate network is formed by sodium alginate under the action of divalent or trivalent metal ions.
Example 2
The gas-sensitive gel of this example was the same as that of example 1 except that the metal salt concentration was replaced with 2 mol/L.
Example 3
The gas-sensitive gel of this example is the same as that of example 1 except that glycerin is further included.
This example was prepared in the same manner as in example 1, except that glycerol was further soaked for 1 hour after the calcium chloride solution was soaked in step S2, to obtain the desired gel.
Comparative example 1
The gas-sensitive gel of this comparative example was the same as in example 1 except that the metal salt concentration was replaced with 0.3 mol/L.
Comparative example 2
The gas-sensitive gel of this comparative example was the same as in example 1 except that the metal salt concentration was replaced with 4 mol/L.
Comparative example 3
The gas-sensitive gel of this comparative example was the same as example 1 except that alginate was replaced with carrageenan.
Performance testing
Co-preparation of NO with the gas-sensitive gel prepared in example 1 and an electrode2The gas sensor comprises a gas sensor, wherein an anode is silver, a cathode is also silver, and the gas sensor comprises the following specific steps:
winding a silver wire (anode) with the diameter of 30-300 mu m to one end of the gas-sensitive gel, and then connecting the silver wire (anode) with the positive electrode of a power supply; winding a silver wire (cathode) with the diameter of 30-300 mu m to the other end of the gas-sensitive gel, and then connecting the silver wire (cathode) with the positive electrode of a power supply, wherein the distance between the positive electrode and the negative electrode is 5-30 mm, and the voltage of an external power supply is 0.2-3V, as shown in figure 1.
When the electrodes at both ends are connected with an external power supplyIf NO exists in the environment to be measured at a certain concentration2，NO2The molecules will adsorb to the cathode and react, the reaction at the cathode being NO2The process of obtaining electrons from molecules and the reaction at the anode is the process of losing electrons from metal material, and this process promotes the charge flow in the loop effectively, so that the current or conductance in the loop is increased, and the change of current or conductance can be used to implement the NO reaction2The gas sensor is provided with a function of detecting NO2The ability of the cell to perform.
As shown in fig. 4, the gas-sensitive gel of this example 1 has a transmittance of more than 75% in the visible light range, and exhibits good transparency.
As shown in fig. 5, the gas-sensitive gel of this example 1 has excellent deformability, and can generate 550% tensile strain, 45 ° bending strain and 360 ° torsional strain.
As shown in FIG. 6a, the gas sensor obtained in this example 1 is sensitive to NO concentration in the order of parts per million (ppm)2Increase in conductance during the response indicates NO2The reaction of (a) promotes charge flow in the loop. The response value and the detected NO2The concentration has good linear relation, which is beneficial to practical application, and as can be seen from figure 6b, the sensitivity is as high as 31.17%/ppm, which shows that the gas sensor prepared by the invention can be used for NO2A significant response is exhibited.
Then the gas-sensitive gel prepared in example 2 is taken to prepare NO together with the electrode2The subsequent test was performed on a gas sensor in which the anode was copper-tin alloy and the cathode was silver.
As shown in FIG. 7a, the gas sensor obtained in example 2 has good sensitivity, and as can be seen from FIG. 7b, the sensitivity is as high as 50.51%/ppm, which is higher than that obtained in example 1. And when the sensor works in a deformation state, the sensor still shows a large response, and shows a great potential for being applied to wearable equipment. In addition, as can be seen from fig. 7c and 7d, the gas sensor has good tensile properties.
As shown in FIG. 8, the gas sensor obtained in example 2 also had excellent selectivity for NO2Production of other gasesThe responses are all less than 3%, which shows that the anti-interference capability is strong.
As shown in fig. 9a, the gas sensor obtained in this example 2 has almost completely disappeared response when the cathode was shielded, and still showed normal response when the anode was shielded, which indicates NO2Adsorption and reaction on the cathode are necessary conditions for generating a response, as shown in fig. 9b, in which the anode material loses electrons and is oxidized; NO on cathode2Electrons are obtained and reduced.
Co-preparation of NO by use of the gas-sensitive gel prepared in example 3 and an electrode2The subsequent test was performed on a gas sensor in which the anode was copper-tin alloy and the cathode was silver.
As shown in fig. 10a to 10d, in the anti-drying and anti-freezing experiments, the gas sensor (soaked with glycerol) obtained in this example 3 showed better moisture retention and anti-freezing performance than the gas sensors (not soaked with glycerol) obtained in the first two examples, the mass loss and resistance change of the gel were delayed, the freezing temperature was reduced, and the gas sensor soaked with glycerol for 30min was frozen at-47 ℃. The gas sensor soaked in the glycerol for 60min does not freeze even at the low temperature of-120 ℃, which shows that the gas sensor can realize the electric conduction within the range from-120 ℃ to room temperature, and the working temperature range is wider.
As shown in fig. 11, the gas sensor obtained in example 3 exhibited a slightly lower response than the gas sensor obtained in example 2, but the sensitivity was still as high as 46.26%/ppm. Shows that the introduction of the glycerol can improve the moisture retention and the freezing resistance at the same time, and the cost is to NO2The sensitivity of (2) is slightly reduced.
As shown in FIG. 12, the gas sensor of example 1, in which both the anode and the cathode were silver, had a response time of 134.5s, a recovery time of 79.5s and a response size of 61.5%, was fabricated as shown in FIG. 13, in which the gas sensor of example 2, in which the anode was made of a copper-tin alloy and the cathode was made of silver, had a response time of 79.7s, a recovery time of 71.3s and a response size of 2ppm NO2The response obtained was about 120%, and it can be seen that the response time and recovery time of example 2 are both reduced, the response sumRecovery is faster and response is larger.
In contrast, the gas-sensitive gel prepared in comparative example 1 can provide less divalent or trivalent metal ions due to the lower concentration of the metal salt, and the sodium alginate is difficult to form a sufficient network. In addition, since the amount of ions is too small, the obtained gel has poor conductivity, and the gas sensor produced is liable to cause large noise during testing. Comparative example 2 due to the high concentration of metal salt, the network formed rapidly and was denser, thus resulting in increased gel strength, decreased toughness, a reduced range of deformation that could be tolerated, and also possibly significant volume expansion. The carrageenan adopted in the comparative example 3 needs to form a network under the action of monovalent metal ions, and at the moment, the monovalent metal ions do not exist in the system, so the carrageenan cannot form the network. The obtained gel is only single-network (polyacrylamide) gel, the mechanical property is poor, even if the carrageenan forms a network by adding univalent metal ions, the obtained polyacrylamide/carrageenan gel can deform to a certain degree but can only be used in a low-stress state, the toughness of the polyacrylamide/carrageenan gel is lower than that of the polyacrylamide/calcium alginate gel, the polyacrylamide/calcium alginate gel can deform to a large degree and can bear stress of more than 500kPa, and in addition, the response and recovery are slowed down.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The gas-sensitive gel is characterized by comprising a polymer network, a solvent in the polymer network and a metal salt, wherein the polymer network is a polyacrylamide-alginate crosslinked network, the metal salt is a divalent and/or trivalent metal salt, and the concentration of the metal salt is 0.5-2 mol/L.
2. The gas-sensitive gel of claim 1, wherein the metal salt is one or more of calcium chloride, magnesium chloride, aluminum chloride, and ferric chloride.
3. The gas-sensitive gel of claim 1, wherein the solvent is water and/or an alcohol solvent.
4. A method of preparing a gas-sensitive gel according to any of claims 1 to 3, comprising the steps of:
uniformly mixing acrylamide, alginate, a solvent, a crosslinking agent, an accelerant and an initiator at room temperature, pouring the obtained solution into a mold, heating to 50-90 ℃, preserving heat for 1-3 hours, cooling to obtain a gel precursor, soaking the gel precursor in an electrolyte for 1-5 hours to obtain the gas-sensitive gel, wherein the mass ratio of the acrylamide to the alginate to the solvent to the crosslinking agent to the accelerant to the initiator is 1: 0.1-0.2: 6-7: 0.0004 to 0.0006: 0.002 to 0.003: 0.005-0.008.
5. The preparation method of claim 4, wherein the mass ratio of the acrylamide to the alginate to the solvent to the cross-linking agent to the accelerator to the initiator is 1: 0.1-0.15: 6.5-7: 0.00045-0.0005: 0.0025 to 0.003: 0.005-0.006.
6. The method according to claim 4, wherein the crosslinking agent is N, N' -methylene acrylamide and/or ethylene glycol dimethacrylate.
7. The production method according to claim 4, wherein the initiator is ammonium persulfate and/or potassium persulfate.
8. Use of the gas-sensitive gel of any one of claims 1 to 3 in the preparation of NO2Use in a gas sensor.
9. NO (nitric oxide)2A gas sensor comprising a gas sensitive gel and electrodes at either end of the gel.
10. NO according to claim 92The application of the gas sensor in preparing wearable electronic devices.
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| CN103396562A (en) * | 2013-07-09 | 2013-11-20 | 西安交通大学 | Preparation method for sodium alginate-acrylamide-based hydrogel |
| CN109490379A (en) * | 2018-12-27 | 2019-03-19 | 中山大学 | Gas sensor and its preparation method of application, equipment and gas sensor |
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