CN115418005A - Preparation method and application of anti-freezing pectin-based conductive hydrogel based on synergistic effect of conductive polymer and multivalent salt ions - Google Patents
Preparation method and application of anti-freezing pectin-based conductive hydrogel based on synergistic effect of conductive polymer and multivalent salt ions Download PDFInfo
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Abstract
The invention discloses a preparation method and application of antifreeze pectin-based conductive hydrogel based on the synergistic effect of a conductive polymer and multivalent salt ions, wherein pectin, carboxymethyl chitosan, methylene bisacrylamide and ammonium persulfate are sequentially dissolved in an acrylamide solution to obtain an acrylamide/pectin-carboxymethyl chitosan solution; adding CaCl 2 Dissolving in the solution; polymerizing pectin/carboxymethyl chitosan-CaCl in a forced air drying oven 2 The polyacrylamide hydrogel is used as a basic skeleton and is placed in CaCl containing pyrrole and dopamine hydrochloride 2 And in-situ synthesizing polypyrrole in the solution to obtain the antifreeze pectin-based conductive hydrogel. The invention effectively solves the problems of poor mechanical property, poor conductivity and no freezing resistance of the traditional conductive hydrogel electrode.
Description
Technical Field
The invention belongs to the technical field of preparation and application of conductive hydrogel, and particularly relates to a preparation method and application of antifreeze pectin-based conductive hydrogel based on synergistic effect of a conductive polymer and multivalent salt ions.
Background
Wearable electronic devices have found wide application in the fields of medical monitoring, electronic skin, flexible touchable displays, and human-computer interaction. By converting mechanical deformation into an electric signal, the signal conversion mode enables human organisms to be connected with traditional electronic equipment, and the life of people is greatly changed. In recent years, hydrogels have been considered as a new material for wearable sensors due to their ideal biocompatibility and flexibility. To date, hydrogel-based sensors have included two main types: the first is the successful preparation of multifunctional ion-conducting sensors by soaking ion-conducting hydrogels in polyelectrolytes or salt ions containing a large number of free ions, such as by simply soaking a double-network hydrogel in a sodium chloride solution. However, these hydrogels have limited conductivity, sensitivity, and environmental stability, which limits their practical applications. Another is an electronically conductive hydrogel by incorporating conductive fillers such as Polyaniline (PANI), graphene/graphene oxide, carbon nanotubes, or MXene. For example, by polymerizing polyaniline in situ on chitosan, an electronic conductive hydrogel is designed, and the hydrogel is sensitive to strain change and can be used as a strain hydrogel based sensor. TENG based on triboelectrification and electrostatic induction, which is proposed by Wangzhong academy in 2012, provides a feasible solution with good development prospect for solving the problems, and is used as a sensor for monitoring human body movement. However, the poor solubility and dispersibility of the conductive fillers may impair the mechanical properties and compatibility of the hydrogel. In general, an ideal hydrogel sensor needs to integrate various functions such as electrical conductivity, good mechanical properties, stretchability, biocompatibility, and the like. However, meeting all requirements in a single electronic device remains a challenge.
Disclosure of Invention
The invention provides a preparation method of antifreeze pectin-based conductive hydrogel based on the synergistic effect of a conductive polymer and multivalent salt ions, and aims to solve the problems of poor mechanical property, poor conductivity and no antifreeze property of the conventional conductive hydrogel electrode.
The invention starts from the design of the antifreeze pectin base conductive hydrogel based on the synergistic effect of the conductive polymer and the multivalent salt ions: acrylamide monomer is adopted to form polyacrylamide chain through spontaneous addition polymerization, the polyacrylamide chain and cross-linking agent methylene bisacrylamide form three-dimensional network through addition reaction, caCl 2 Ca in (1) 2+ Ca is formed as a cross-linking point to form an eggshell structure with the carboxyl group of galacturonic acid in pectin that is not esterified 2+ -COO-coordination complex network; forming a physical cross-linked network with carboxyl on the carboxymethyl chitosan, wherein a plurality of networks are mutually interpenetrated, and further effectively improving the mechanical property of the carboxymethyl chitosan, and the formed multi-network hydrogel is a basic frame and is placed in CaCl containing pyrrole and dopamine hydrochloride 2 In solutionThe hydrogel has more excellent conductivity by the mode of in-situ polymerization of polypyrrole; high concentration of Ca 2+ The prepared pectin-based high-performance anti-freezing and anti-drying hydrogel has certain freezing resistance, is applied to a flexible friction nano generator as an electrode to test the electrical output performance of the flexible friction nano generator, and the actual application value of the flexible friction nano generator is investigated.
The invention adopts the following technical scheme to solve the technical problems, and the preparation method of the antifreeze pectin-based conductive hydrogel based on the synergistic effect of the conductive polymer and the multivalent salt ions is characterized by comprising the following specific steps of:
step S1: dissolving 9.94g of acrylamide in 40mL of deionized water to prepare an acrylamide solution, and then sequentially adding 0.005g of methylene bisacrylamide, 0.2g of pectin, 0.3g of carboxymethyl chitosan and 0.24g of ammonium persulfate to fully dissolve the materials to obtain an acrylamide/chitosan-pectin solution;
step S2: adding 0.5g of CaCl 2 Placing into the acrylamide/chitosan-pectin solution obtained in the step S1, performing ultrasonic treatment after full dissolution, dripping into a glass ware by using a needle tube, and drying in a forced air drying oven at 60 ℃ to obtain pectin/carboxymethyl chitosan-CaCl 2 Polyacrylamide hydrogel;
and step S3: dissolving 0.048 to 0.193g of pyrrole monomer and 0.05 to 0.2g of dopamine hydrochloride in 10mL of deionized water at 4 ℃, uniformly stirring and mixing, and then adding the pectin/carboxymethyl chitosan-CaCl prepared in the step S2 2 Soaking polyacrylamide hydrogel at 4 deg.C, taking out the hydrogel, and storing in a sealed container at 4 deg.C to make polypyrrole (Ppy) uniformly permeate into pectin-based hydrogel;
and step S4: soaking the hydrogel obtained in the step S3 in FeCl 3 And CaCl 2 In an aqueous solution of (1), wherein FeCl 3 The molar concentration of the active component is 0.089mol/L, caCl 2 The mass percentage of the anti-freezing pectin-based conductive hydrogel is 60wt%, and the anti-freezing pectin-based conductive hydrogel is obtained by soaking at 4 ℃.
The invention discloses application of antifreeze pectin-based conductive hydrogel as an electrode of a friction nano generator, which is characterized by comprising the following specific steps: placing the friction nano-generator electrode prepared from the anti-freezing pectin-based conductive hydrogel on the surface of a friction layer, connecting a lead between the hydrogel and the friction layer, covering the same friction layer on the opposite surface to form a sandwich structure, and sealing the port at four ends by using flexible double-sided adhesive to obtain the anti-freezing pectin-based conductive hydrogel-based friction nano-generator
Further, the friction layer is polydimethylsiloxane prepared by mixing Sylgard 184 monomer and Sylgard 184 curing agent according to a mass ratio of 10.
Compared with the prior art, the invention has the following beneficial effects:
1. the acrylamide adopted by the invention forms a polyacrylamide chain through spontaneous addition polymerization, and the polyacrylamide chain and a cross-linking agent methylene bisacrylamide form a three-dimensional network through addition reaction. In the metal salt ion CaCl 2 Forming Ca with carboxyl group of galacturonic acid in pectin which is not esterified 2+ the-COO-coordination complex network and the carboxyl on the carboxymethyl chitosan form a physical cross-linked network, and various networks are mutually interpenetrated, so that the mechanical property of the hydrogel is effectively improved, and the tensile property can reach about 2800%.
2. The method adopts an in-situ polymerization polypyrrole mode, and the conductive polymer and the multivalent salt ions have synergistic effect, so that the conductivity of the hydrogel electrode is further improved, the conductivity is improved from 5.417m/s to 8.085m/s, and the tensile property can also reach 800%; high concentration of Ca 2+ The hydrogel has good freezing resistance and can be normally used at the low temperature of 24 ℃ below zero.
3. The invention adopts a closed sandwich structure, improves the dryness resistance of the hydrogel by adopting a sandwich structure of a friction layer-hydrogel electrode-friction layer and a mode of sealing a port by using flexible double-sided adhesive, and controls the water loss rate of the hydrogel within 3.98 percent within 30 days.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a high-performance anti-freezing dry-resistant hydrogel friction nanogenerator in example 6;
description of the drawings: 1-polydimethylsiloxane film, 2-antifreeze pectin-based conductive hydrogel and 3-lead;
FIG. 2 is a stress-strain test curve of an anti-freeze pectin-based conductive hydrogel prepared with simple salt ions;
FIG. 3 is a stress-strain test curve of the anti-freeze pectin-based conductive hydrogel prepared in example 3;
FIG. 4 is a graph of the conductivity of the anti-freeze pectin-based conductive hydrogels prepared in examples 1-5;
FIG. 5 is a graph of the water loss resistance of the antifreeze pectin-based conductive hydrogel prepared in example 6;
FIG. 6 is a graph of the voltage output signal of the anti-freeze pectin-based conductive hydrogel triboelectric nanogenerator prepared in example 6;
FIG. 7 is a graph of the current output signal of the antifreeze pectin-based conductive hydrogel triboelectric nanogenerator prepared in example 6;
FIG. 8 is a graph of the transferred charge signals of the antifreeze pectin-based conductive hydrogel triboelectric nanogenerator prepared in example 6;
FIG. 9 is a graph of the conductivity of the anti-freeze pectin-based conductive hydrogel prepared in example 6 before and after freezing;
fig. 10 is a graph of voltage output signals before and after freezing of the anti-freeze pectin-based conductive hydrogel triboelectric nanogenerator prepared in example 6.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be understood that the scope of the subject matter of the present invention is limited to the examples below, and any technique realized based on the above contents of the present invention falls within the scope of the present invention.
Example 1
Step S1: dissolving 9.94g of acrylamide in 40mL of deionized water, and then adding 0.2g of pectin, 0.3g of carboxymethyl chitosan, 0.005g of methylene bisacrylamide and 0.24g of ammonium persulfate to fully dissolve the materials to obtain an acrylamide/pectin-carboxymethyl chitosan solution, wherein the rotating speed is 1500r/min;
step S2: adding 0.5g of CaCl 2 Adding into the acrylamide/pectin-carboxymethyl chitosan solution obtained in the step S1 at the rotating speed of 600r/min, and adding into the solution after full dissolutionPerforming ultrasonic treatment for 30min, dripping into glassware with needle tube, and drying in forced air drying oven at 60 deg.C for 1 hr to obtain pectin/carboxymethyl chitosan-CaCl 2 Polyacrylamide hydrogel;
and step S3: dissolving 0.048g of pyrrole monomer in 10mL of deionized water at 4 ℃, uniformly stirring, and adding the pectin/carboxymethyl chitosan-CaCl obtained in the step S2 2 Soaking the polyacrylamide hydrogel at 4 deg.C for 12h, taking out the hydrogel, and storing in a sealed empty container at 4 deg.C for 3h to allow PPy to uniformly permeate into the pectin-based hydrogel;
and step S4: soaking the hydrogel obtained in the step S3 in FeCl 3 (0.089 mol/L) and CaCl 2 Soaking in 60wt% water solution at 4 deg.c to obtain antifreezing pectin-based conductive hydrogel with conductivity of 5.417m/s.
Example 2
Step S1: step S1: dissolving 9.94g of acrylamide in 40mL of deionized water, and then adding 0.2g of pectin, 0.3g of carboxymethyl chitosan, 0.005g of methylene bisacrylamide and 0.24g of ammonium persulfate to fully dissolve the materials to obtain an acrylamide/pectin-carboxymethyl chitosan solution, wherein the rotating speed is 1500r/min;
step S2: adding 0.5g of CaCl 2 Adding into the acrylamide/pectin-carboxymethyl chitosan solution obtained in step S1 at a rotation speed of 600r/min, dissolving completely, placing into an ultrasonic treatment tank for 30min, dripping into a glass ware through a needle tube, and drying in a forced air drying oven at 60 deg.C for 1h to obtain pectin/carboxymethyl chitosan-CaCl 2 Polyacrylamide hydrogel;
and step S3: dissolving 0.048g of pyrrole monomer and 0.05g of dopamine hydrochloride in 10mL of deionized water at 4 ℃, uniformly stirring, and adding the pectin/carboxymethyl chitosan-CaCl obtained in the step S2 2 Soaking the polyacrylamide hydrogel at 4 deg.C for 12h, taking out the hydrogel, and storing in a sealed empty container at 4 deg.C for 3h to allow PPy to uniformly permeate into the pectin-based hydrogel;
and step S4: soaking the hydrogel obtained in the step S3 in FeCl 3 (0.089 mol/L) and CaCl 2 (60 wt%) in water solution, soaking at 4 deg.C to obtain antifreeze pectin-based conductive hydrogel,the conductivity was 6.678m/s.
Example 3
Step S1: dissolving 9.94g of acrylamide in 40mL of deionized water, and then adding 0.2g of pectin, 0.3g of carboxymethyl chitosan, 0.005g of methylene bisacrylamide and 0.24g of ammonium persulfate to fully dissolve the materials to obtain an acrylamide/pectin-carboxymethyl chitosan solution, wherein the rotating speed is 1500r/min;
step S2: adding 0.5g of CaCl 2 Adding into the acrylamide/pectin-carboxymethyl chitosan solution obtained in step S1 at a rotation speed of 600r/min, dissolving completely, placing into an ultrasonic treatment tank for 30min, dripping into a glass ware through a needle tube, and drying in a forced air drying oven at 60 deg.C for 1h to obtain pectin/carboxymethyl chitosan-CaCl 2 Polyacrylamide hydrogel;
and step S3: dissolving 0.097g of pyrrole monomer and 0.1g of dopamine hydrochloride in 10mL of deionized water at 4 ℃, uniformly stirring and mixing, and then adding the pectin/carboxymethyl chitosan-CaCl obtained in the step S2 2 Soaking the polyacrylamide hydrogel at 4 deg.C for 12h, taking out the hydrogel, and storing in a sealed empty container at 4 deg.C for 3h to allow PPy to uniformly permeate into the pectin-based hydrogel;
and step S4: soaking the hydrogel obtained in the step S3 in FeCl 3 (0.089 mol/L) and CaCl 2 (60 wt%) in the water solution, and soaking at 4 deg.C to obtain the antifreeze pectin-based conductive hydrogel with conductivity of 8.085m/s.
Example 4
Step S1: dissolving 9.94g of acrylamide in 40mL of deionized water, and then adding 0.2g of pectin, 0.3g of carboxymethyl chitosan, 0.005g of methylene bisacrylamide and 0.24g of ammonium persulfate to fully dissolve the materials to obtain an acrylamide/pectin-carboxymethyl chitosan solution, wherein the rotating speed is 1500r/min;
step S2: adding 0.5g of CaCl 2 Adding into the acrylamide/pectin-carboxymethyl chitosan solution obtained in step S1 at a rotation speed of 600r/min, dissolving sufficiently, placing into an ultrasonic treatment device for 30min, dripping into a glass ware through a needle tube, and drying in a forced air drying oven at 60 deg.C for 1h to obtain pectin/carboxymethyl chitosan-CaCl 2 Polyacrylamide hydrogel;
and step S3: dissolving 0.145g of pyrrole monomer and 0.15g of dopamine hydrochloride in 10mL of deionized water at 4 ℃, uniformly stirring and mixing, and then adding the pectin/carboxymethyl chitosan-CaCl obtained in the step S2 2 Soaking the polyacrylamide hydrogel at 4 deg.C for 12h, taking out the hydrogel, and storing in a sealed empty container at 4 deg.C for 3h to allow PPy to uniformly permeate into the pectin-based hydrogel;
and step S4: soaking the hydrogel obtained in the step S3 in FeCl 3 (0.089 mol/L) and CaCl 2 (60 wt%) in water solution, and soaking at 4 deg.C to obtain the antifreeze pectin-based conductive hydrogel with conductivity of 7.568m/s.
Example 5
Step S1: dissolving 9.94g of acrylamide in 40mL of deionized water, and then adding 0.2g of pectin, 0.3g of carboxymethyl chitosan, 0.005g of methylene bisacrylamide and 0.24g of ammonium persulfate to fully dissolve the materials to obtain an acrylamide/pectin-carboxymethyl chitosan solution, wherein the rotating speed is 1500r/min;
step S2: adding 0.5g of CaCl 2 Adding into the acrylamide/pectin-carboxymethyl chitosan solution obtained in step S1 at a rotation speed of 600r/min, dissolving completely, placing into an ultrasonic treatment tank for 30min, dripping into a glass ware with a needle tube, and drying in a forced air drying oven at 60 deg.C for 1 hr to obtain pectin/carboxymethyl chitosan-CaCl 2 A polyacrylamide hydrogel;
and step S3: dissolving 0.193g of pyrrole monomer and 0.2g of dopamine hydrochloride in 10mL of deionized water at 4 ℃, uniformly stirring and mixing, and then adding the pectin/carboxymethyl chitosan-CaCl obtained in the step S2 2 Soaking the polyacrylamide hydrogel at 4 deg.C for 12h, taking out the hydrogel, and storing in a sealed empty container at 4 deg.C for 3h to allow PPy to uniformly permeate into the pectin-based hydrogel;
and step S4: soaking the hydrogel obtained in the step S3 in FeCl 3 (0.089 mol/L) and CaCl 2 Soaking in 60wt% water solution at 4 deg.c to obtain the antifreezing pectin-based conductive hydrogel with conductivity of 7.079m/s.
Example 6
The flexible friction nano generator is characterized in that an anti-freezing pectin-based conductive hydrogel 2 is used as an electrode, and PDMS (polydimethylsiloxane film 1) is a friction layer formed by mixing Sylgard 184 monomer and Sylgard 184 curing agent according to a mass ratio of 10. Specifically, the prepared antifreeze pectin-based conductive hydrogel (example 4) is placed on the surface of a friction layer, a lead 3 is connected between the hydrogel and the friction layer, then the same friction layer is covered on the opposite surface to form a sandwich structure, and the flexible double-sided adhesive tape is used for sealing the port at four ends, so that the pectin-based antifreeze anti-dry hydrogel-based friction nano-generator is obtained. The thickness of the friction layer is 1mm, and the thickness of the hydrogel electrode is 3mm. A6514 system static electricity meter is adopted to measure that the open-circuit voltage of the electrode based on the pectin-based anti-freezing and anti-drying hydrogel flexible friction nano generator is 320V, the short-circuit current is 9 mu A, and the transfer charge is 70nC.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (3)
1. The preparation method of the anti-freezing pectin-based conductive hydrogel based on the synergistic effect of the conductive polymer and the multivalent salt ions is characterized by comprising the following specific steps of:
step S1: dissolving 9.94g of acrylamide in 40mL of deionized water to prepare an acrylamide solution, and then sequentially adding 0.005g of methylene bisacrylamide, 0.2g of pectin, 0.3g of carboxymethyl chitosan and 0.24g of ammonium persulfate to fully dissolve the materials to obtain an acrylamide/chitosan-pectin solution;
step S2: adding 0.5g of CaCl 2 Placing into the acrylamide/chitosan-pectin solution obtained in the step S1, performing ultrasonic treatment after full dissolution, dripping into a glass ware by using a needle tube, and drying in a forced air drying oven at 60 ℃ to obtain pectin/carboxymethyl chitosan-CaCl 2 Polyacrylamide hydrogel;
and step S3: dissolving 0.048 to 0.193g of pyrrole monomer in 10mL of deionized water at 4 DEG CAnd 0.05 to 0.2g of dopamine hydrochloride, stirring and mixing uniformly, and then adding the pectin/carboxymethyl chitosan-CaCl prepared in the step S2 2 Soaking polyacrylamide hydrogel at 4 deg.C, taking out the hydrogel, storing in a sealed empty container at 4 deg.C, and allowing polypyrrole to uniformly penetrate into pectin-based hydrogel;
and step S4: soaking the hydrogel obtained in the step S3 in FeCl 3 And CaCl 2 In an aqueous solution of (1), wherein FeCl 3 The molar concentration of the catalyst is 0.089mol/L, caCl 2 The mass percentage of the anti-freezing pectin-based conductive hydrogel is 60wt%, and the anti-freezing pectin-based conductive hydrogel is obtained by soaking at 4 ℃.
2. The application of the antifreeze pectin-based conductive hydrogel prepared by the method of claim 1 as an electrode of a friction nano generator is characterized by comprising the following steps: and placing the electrode of the friction nano-generator prepared from the anti-freezing pectin-based conductive hydrogel on the surface of a friction layer, connecting a lead between the hydrogel and the friction layer, covering the same friction layer on the opposite surface to form a sandwich structure, and sealing the port at the four ends by using flexible double-sided adhesive to obtain the anti-freezing pectin-based conductive hydrogel-based friction nano-generator.
3. Use according to claim 2, characterized in that: the friction layer is polydimethylsiloxane, the polydimethylsiloxane is prepared by mixing Sylgard 184 monomer and Sylgard 184 curing agent according to the mass ratio of 10.
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| CN115753933A (en) * | 2022-12-22 | 2023-03-07 | 中国热带农业科学院南亚热带作物研究所 | Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode |
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|---|---|---|---|---|
| CN115753933A (en) * | 2022-12-22 | 2023-03-07 | 中国热带农业科学院南亚热带作物研究所 | Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode |
| CN115753933B (en) * | 2022-12-22 | 2023-08-11 | 中国热带农业科学院南亚热带作物研究所 | Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode |
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