CN115684302A - Method for preparing flexible pH sensor through ink-jet printing - Google Patents
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Abstract
The invention discloses a method for preparing a flexible pH sensor by ink-jet printing, which comprises the following steps: providing Ag ink, au ink, PANI ink, feCl 3 Inks and PVB inks; printing Ag ink on a flexible substrate at intervals by ink jet, and drying to obtain a working electrode and a reference electrode; printing Au ink on the working electrode in an ink-jet manner, drying, then printing PANI ink in an ink-jet manner, and drying to obtain the working electrode based on Ag/Au/PANI; ink jet printing FeCl on the reference electrode 3 Ink, drying, then carrying out ink-jet printing on PVB ink, and drying to obtain the ink based on Ag/FeCl 3 PVB, namely preparing the flexible pH sensor. The method can realize the in-situ large-scale mass production and manufacture of the flexible pH sensor, ensure the repeatability of the sensor and reduce the error of the sensitivity of each sensor to the maximum extent; the prepared pH sensor has good selectivity to hydrogen ions, high stability and high response speed,the device is particularly suitable for real-time detection of pH of sweat, wounds and the like in wearable equipment.
Description
Technical Field
The invention relates to the technical field of sensors, in particular to a method for preparing a flexible pH sensor through ink-jet printing.
Background
The pH sensor can be widely applied to various fields, such as water area detection, industrial production, medicine detection and the like, and with the continuous development of science and technology and the continuous attention of people on the health and safety of people, the detection of the pH value of the skin is also very important, especially in the aspects of wound healing of diabetes patients and the like. The pH is an important parameter in response to dynamic changes in the wound and the healing process, and normal wound healing has a pH between 4.5 and 6.5, above which inflammatory wounds have a pH and can lead to bacterial growth. Meanwhile, the pH value of the skin may represent the whole acid-base equilibrium state of the body, and can be even used for potential disease diagnosis. At present, a plurality of methods for detecting pH at home and abroad are available, such as: pH test paper method, indicator method, pH meter method, potential method. However, the pH test paper needs to be subjectively compared with the color of the standard colorimetric method by naked eyes, the error is large, and the accuracy is low; the pH meter method can only obtain a certain range of pH value and has poor stability; the pH meter method is digital equipment with good accuracy and high sensitivity, but the equipment cannot be miniaturized. Both of these methods are not conducive to pH continuity detection, such as in human-based wearable devices.
The potentiometry has certain advantages in the directions of accuracy, miniaturization, rapid detection, continuous detection and the like. The potential method pH sensor based on polyaniline usually adopts an electroplating method to electroplate aniline into polyaniline attached to an electrode, but the electroplating time is difficult to accurately control and the randomness of the electroplating process is difficult to realize, the mass production is not facilitated, the integral difference of devices is large, and the repeatability is difficult to effectively solve. For example, patent publication No. CN106706734B discloses a method for processing a pH-sensitive electrode with polyaniline response, in which synthesized polyaniline particles are cured on the electrode by ultraviolet light, thereby forming a pH-sensitive polymer thin film electrode. Although this method yields a sensitive pH sensor, similarly, for mass production, the polyaniline solution added dropwise during the thermal curing process is not easy to control the amount and height of the addition, the solution diffusion area, and the like, resulting in a certain sensitivity error between each sensor.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for preparing a flexible pH sensor by ink-jet printing, and aims to solve the problems that the prior method for preparing the flexible pH sensor is difficult to realize better repeatability and sensitivity errors exist among prepared sensors.
The technical scheme of the invention is as follows:
a method for preparing a flexible pH sensor by inkjet printing, comprising the steps of:
silver (Ag) ink, gold (Au) ink, polyaniline (PANI) ink, and ferric chloride (FeCl) 3 ) Inks and polyvinyl butyral (PVB) inks;
printing Ag ink on a flexible substrate at intervals by ink jet, and drying to obtain a working electrode and a reference electrode;
printing Au ink in an ink-jet mode in the working electrode working area, drying, then printing PANI ink in an ink-jet mode, and drying to obtain the working electrode based on Ag/Au/PANI;
ink-jet printing FeCl on the reference electrode working area 3 Ink, drying, then ink-jet printing PVB ink, drying to obtain the Ag/FeCl-based ink 3 And preparing an Ag/AgCl/PVB reference electrode of PVB to obtain the flexible pH sensor.
The method for preparing the flexible pH sensor by ink-jet printing comprises the following steps of:
polyvinylpyrrolidone (PVP) was added to tetrachloroauric acid tetrahydrate (HAuCl) with continuous stirring 4 ·4H 2 O) water solution to obtain a first mixed solution;
in sodium borohydride (NaBH) 4 ) Adding an alkaline solution into the solution, stirring, refrigerating and cooling to obtain a second mixed solution;
dropwise adding the second mixed solution into the first mixed solution, and reacting to obtain Au nanoparticles;
and adding the Au nano particles into a third mixed solution consisting of organic alcohol and deionized water, and performing ultrasonic redispersion to obtain the Au ink.
The method for preparing the flexible pH sensor by ink-jet printing is disclosed, wherein the HAuCl 4 ·4H 2 The molar concentration of the O aqueous solution is 10-50 millimoles; the molar concentration of PVP is 10-50 millimole; the NaBH 4 The molar concentration of the solution is 1-5 mol, and the molar concentration of the NaOH solution is 1-5 mol.
The method for preparing the flexible pH sensor by ink-jet printing comprises the following steps:
mixing aniline solution and ammonium persulfate solution with equal volume under the condition of existence of hydrochloric acid, reacting to prepare PANI solution, and centrifuging the PANI solution to remove supernatant to prepare PANI nano-wires;
and mixing the PANI nano-wire with deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion to obtain the PANI ink.
The method for preparing the flexible pH sensor by ink-jet printing comprises the following steps of setting ink-jet printing voltage to be 20-40V and ink-jet printing spacing to be 5-30 micrometers in the ink-jet printing process; the ink jet printing height is 500-2000 microns.
The method for preparing the flexible pH sensor by ink-jet printing comprises the following steps of in the ink-jet printing process, drying conditions of each printed layer are as follows: the temperature is 40-60 ℃ and the time is 0.2-0.6 h.
The method for preparing the flexible pH sensor through ink-jet printing comprises the steps of mixing Au ink and ethylene glycol according to a volume ratio of 1.2-1, and forming a mixture with the viscosity of 8-12 centipoises and the density of 1.01-1.2kg/m, wherein the volume ratio of the Au ink to the ethylene glycol is as follows 3 And the surface tension of the Au printing liquid is 25-35 mN/m.
The method for preparing the flexible pH sensor through ink-jet printing comprises the steps of mixing PANI ink and glycol according to a volume ratio of 1 3 PANI printing liquid with surface tension of 30-44 mN/m.
The method for preparing the flexible pH sensor by ink-jet printing comprises the step of ink-jet printing FeCl on the reference electrode 3 FeCl is first added before ink 3 The ink is mixed with ethylene glycol according to a volume ratio of 1.1-1 3 FeCl with surface tension of 26-38mN/m 3 And (4) printing liquid.
The method for preparing the flexible pH sensor through ink-jet printing comprises the step of mixing PVB ink and glycerol according to a volume ratio of 1 3 PVB printing liquid with surface tension of 68-80 mN/m.
The invention discloses a flexible pH sensor, which is prepared by adopting the preparation method of the flexible glucose sensor.
Has the advantages that: the invention adopts a complete ink-jet printing mode to print the electrode and various functional layers of the pH sensor, only needs to reasonably control the size of particles or nano wires in the ink and optimize the surface tension, density and viscosity of the ink. The method provided by the invention is simple and convenient, the personalized electrode pattern can be designed, the cost is low, the prepared pH sensor has good selectivity on hydrogen ions, high stability and high response speed, and the method is particularly suitable for real-time detection of pH of sweat, wounds and the like in wearable equipment.
Drawings
Fig. 1 is a flow chart of a method for manufacturing a flexible pH sensor by inkjet printing according to the present invention.
Fig. 2 is an SEM image of Au ink prepared in example 1 printed on a flexible PET substrate.
Fig. 3 is an SEM image of PANI ink prepared in example 1 printed on a flexible PET substrate.
FIG. 4 is a timing diagram of the voltage pulses of the nozzles optimized for ink-jet printing of different inks according to example 1.
FIG. 5 is a graph of voltage-time (v-t) measurements at room temperature at pH 4-7 for a pH sensor prepared in example 1.
FIG. 6 is a graph of a linear fit of steady state voltage values for the pH sensor prepared in example 1.
Fig. 7 is a selectivity test chart of the pH sensor prepared in example 1.
Detailed Description
The invention provides a method for preparing a flexible pH sensor by ink-jet printing, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flowchart illustrating a method for manufacturing a flexible pH sensor by inkjet printing according to a preferred embodiment of the present invention, as shown in the figure, the method includes the steps of:
s10, providing Ag ink, au ink, PANI ink and FeCl 3 Inks and PVB inks;
s20, ink-jet printing Ag ink on the flexible substrate at intervals, and drying to obtain a working electrode and a reference electrode;
s30, performing ink-jet printing on Au ink in the working area of the working electrode, drying, then performing ink-jet printing on PANI ink, and drying to obtain the working electrode based on Ag/Au/PANI;
s40, ink-jet printing FeCl on the working area of the reference electrode 3 Ink, drying, then ink-jet printing PVB ink, drying to obtain the Ag/FeCl-based ink 3 PVB, namely preparing the flexible pH sensor.
The embodiment provides a method for preparing a flexible pH sensor by adopting in-situ complete ink-jet printing, which solves the problem that good repeatability is difficult to realize in the traditional manufacturing process of a polyaniline-based pH sensor; in addition, the method can realize in-situ large-scale mass production and manufacture only by reasonably controlling the size of the nano particles or nano wires in the ink and optimizing the surface tension and viscosity of the ink, the printing parameters are easy to control, the repeatability of the sensors can be ensured, and the error of the sensitivity among the sensors can be reduced to the greatest extent. The method provided by the embodiment is simple and convenient, the personalized electrode pattern can be designed, the cost is low, the selectivity of the prepared pH sensor on hydrogen ions is good, the stability is high, the response speed is high, and the method is particularly suitable for real-time detection of pH of sweat, wounds and the like in wearable equipment.
In some embodiments, the flexible substrate may be a polyethylene terephthalate (PET) substrate, but is not limited thereto. Taking printing Ag ink on a PET substrate as an example, the method comprises the following steps: firstly, washing a PET flexible substrate by using deionized water, acetone and isopropanol, and drying by using a nitrogen gun; then leading in the personalized pattern through a printer, and printing Ag ink through an ink-jet printing device; and finally drying at 40-60 ℃ for 0.5-1.5 hours to ensure that the solvent is completely evaporated, and preparing the electrode.
In this embodiment, the number of layers of the printed Ag ink is 1-3. The ink jet printing apparatus is a Fujifilm Dimatix DMP-2800inkjet printer, but is not limited thereto; the nozzle of the ink box can select ink with different printing capacities such as 1 picoliter, 10 picoliters and the like, and the aperture of the nozzle is 10-21.4 microns and the like; the Ag ink is NovaCentrix JS-B25HV, but is not limited to the NovaCentrix JS-B25 HV; in the ink-jet printing process, the duration, level and conversion rate in the voltage pulse timing diagram of the spray head are continuously adjusted and optimized to obtain better printing quality; deionized water, isopropanol or acetone solution is needed to be used for carrying out ultrasonic cleaning on the ink box after ink-jet printing, so that the ink box is prevented from being blocked.
In some embodiments, the preparation of the Au ink comprises the steps of: PVP was added to HAuCl with stirring 4 ·4H 2 In an O aqueous solution to obtain a first mixed solution; in NaBH 4 Adding an alkaline solution into the solution, stirring, and then placing the solution in a refrigerator for refrigeration and cooling to obtain a second mixed solution; dropwise adding the second mixed solution into the first mixed solution, and reacting to obtain Au nanoparticles; and adding the Au nano particles into a third mixed solution consisting of organic alcohol and deionized water, and performing ultrasonic redispersion to obtain the Au ink.
In this example, the HAuCl 4 ·4H 2 The molar concentration of the O aqueous solution is 10-50 millimoles; the molar concentration of PVP is 10-50 millimole; the NaBH 4 The molar concentration of the solution is 1-5 mol, and the molar concentration of the alkaline solution is 1-5 mol. In the process of preparing the Au nano-particles, the agglomeration of the Au nano-particles can be effectively prevented by adding PVP; the reaction time of the first mixed solution and the second mixed solution is 4 to 24 hours, but is not limited thereto. In this embodiment, the alkaline solution may be a potassium hydroxide solution, a sodium hydroxide solution, or the like.
In some embodiments, the Au ink is mixed with ethylene glycol at a volume ratio of 1.2 to 1 3 Au printing liquid with the surface tension of 25-35 mN/m; and then injecting the Au printing liquid into an ink box for ink-jet printing.
In this embodiment, the number of printed Au ink layers is 1-40, and after each printed Au ink layer, the printed Au ink layer is dried at 40-60 ℃ for 0.2-0.6 hour.
In some embodiments, the preparation of the PANI ink comprises the steps of: mixing aniline solution and Ammonium Persulfate (APS) solution with equal volume under the condition of existence of hydrochloric acid, reacting to prepare PANI solution, and centrifuging the PANI solution to remove supernatant fluid to prepare PANI nano wires; and mixing the PANI nano-wire with deionized water, adding Sodium Dodecyl Sulfate (SDS) and then performing ultrasonic dispersion to prepare the PANI ink.
In this example, the aniline solution has a molar concentration of 0.05 to 0.2 millimole, the hydrochloric acid has a molar concentration of 0.5 to 2 molar, and the ammonium persulfate solution has a concentration of 0.01 to 0.2 molar. In this embodiment, the addition of SDS may improve the stability of the PANI ink. In the embodiment, aniline and ammonium persulfate react for 12-48 hours under the condition of hydrochloric acid to generate PANI solution, and in the process of centrifuging the PANI solution, the rotating speed of a centrifuge is 4000-6000 revolutions per minute, the time of each centrifugation is 0.4-1 hour, and the centrifugation times are 1-4 times, so that the PANI nanowire is obtained.
In some embodiments, ink-jet printing PANI ink on the working electrodeBefore, the PANI ink is mixed with ethylene glycol according to a volume ratio of 1 3 PANI printing liquid with the surface tension of 30-44 mN/m; and then injecting the Au printing liquid into an ink box for ink-jet printing.
In this embodiment, the number of printed PANI ink layers is 1-40, and each printed layer is dried at 40-60 ℃ for 0.2-0.6 hour.
In some embodiments, the FeCl 3 The ink being FeCl 3 An aqueous solution having a concentration of 0.1 to 0.5 mol. Ink-jet printing FeCl on the reference electrode 3 FeCl is first added before ink 3 The ink is mixed with ethylene glycol according to a volume ratio of 1.1-1 3 FeCl with surface tension of 26-38mN/m 3 Printing liquid; then the FeCl is added 3 The printing liquid is injected into the ink box to perform ink-jet printing.
In this embodiment, feCl is printed 3 The number of layers of the ink is 1-40, and after each layer is printed, the ink is dried at the temperature of 40-60 ℃ for 0.2-0.6 hour.
In some embodiments, the preparation of the PVB ink includes the steps of: and dissolving the PVB solution and the excessive NaCl in the methanol solvent, and uniformly stirring to obtain a supernatant, namely the required PVB ink. In this example, the molar concentration of the PVB solution is from 0.5 to 2 molar; the molar concentration of NaCl is 0.5-2 mol.
In some embodiments, the PVB ink is mixed with glycerin in a volume ratio of 1 3 PVB printing liquid with surface tension of 68-80 mN/m; the PVB printing fluid is then injected into an ink cartridge for ink-jet printing.
In the implementation, the number of printed PVB ink layers is 1-40, and after each printed layer, the printed PVB ink layer is dried at the temperature of 40-60 ℃ for 0.2-0.6 hour.
In some embodiments, during the ink-jet printing process, the ink-jet printing voltage is set to be 20-40V, and the ink-jet printing pitch is 5-30 micrometers; the ink jet printing height is 500-2000 microns. In the ink-jet printing process, better printing quality can be obtained by continuously adjusting and optimizing the conditions.
In some embodiments, a flexible pH sensor is also provided, which is made using the above-described method of making a flexible glucose sensor of the invention.
The invention is further illustrated by the following specific examples:
example 1
1. Preparation of Au ink:
will contain 0.05 g of HAuCl 4 ·4H 2 Rapidly stirring 7.5 ml of water solution of O at normal temperature, then adding 0.04 g of PVP, mixing and stirring for 0.5 hour; in 5 ml of 1 mol NaBH 4 Adding 100 microliter of 1 mol NaOH into the solution, stirring for 10 minutes, and then placing the solution in a refrigerator for refrigerating for 30 minutes to less than 5 ℃. Subsequently, to HAuCl containing PVP 4 300 microliter NaBH is dripped into the aqueous solution 4 And mixing the solution with NaOH, and stirring the mixture for 12 hours at room temperature to obtain the Au nano-particle solution generated by reduction. The solution was poured into a centrifuge tube and centrifuged at 6000 rpm for 0.5 hour to remove the supernatant. Then 15 ml of deionized water is added for centrifugation again, the supernatant is removed, and finally Au nanoparticles are obtained at the bottom. To the Au nanoparticles, 1.5 ml of isopropyl alcohol, 3.5 ml of deionized water solution was added, and ultrasonic redispersion was performed for 0.5 hour to obtain an ink. The nanostructure is shown in fig. 2.
2. Preparation of PANI ink:
10 ml of an aqueous solution containing 0.1 mol of aniline and 1 mol of hydrochloric acid (HCl) and an aqueous solution containing 0.25 mol of APS and 1 mol of HCl were prepared, respectively, and stirred at room temperature for 30 minutes; the APS solution was then poured into the aniline solution and the mixed solution shaken vigorously for 30 seconds and stirred at room temperature for 18 hours to give the resultant PANI solution. The solution was poured into a centrifuge tube and centrifuged at 6000 rpm for 0.5 hour to remove the supernatant. Then 20 ml of deionized water is added for centrifugation again, the supernatant is removed, and finally the PANI nanowire is obtained at the bottom. To the PANI nano was added 10 ml of deionized water solution and gently shaken well. After that, 10 mg of SDS was added to the solution, and it was completely dissolved by sonication for 30 minutes to obtain an ink. The nanostructure is shown in fig. 3.
3. Preparing PVB ink:
10 ml of a methanol solution containing 0.8 mol of PVB and 0.8 mol of NaCl was prepared, stirred at room temperature for 30 minutes, and the bottom precipitate was removed to obtain a PVB ink.
4、FeCl 3 Preparation of ink:
FeCl 3 the aqueous solution was stirred at room temperature for 30 minutes at a concentration of 0.1 mol.
5. Preparing an in-situ full ink-jet printing pH sensor:
washing the PET flexible substrate with deionized water, acetone and isopropanol, and blow-drying with a nitrogen gun; selecting an ink box which has a printing nozzle diameter of about 21.4 micrometers and contains 16 nozzles in total and has a printing capacity of 10 picoliters, and introducing a working electrode with a diameter of 3 millimeters and a reference electrode pattern with a diameter of 5 millimeters through a printer; 0.8 ml of Ag ink is taken out, filtered by a 0.25 micron filter plug and injected into the ink box, the printing interval is 20 microns, the printing voltage is 26 volts, the number of printing layers is 1, the printing height is 1000 microns, and a voltage pulse timing chart of the spray head is shown in figure 4. Preparing a working electrode and a reference electrode by ink-jet printing silver ink, and drying at 60 ℃ for 1 hour to ensure that the solvent is completely evaporated;
taking out 0.8 ml of mixed solution with the volume ratio of the Au ink to the ethylene glycol being 1.5, performing ultrasonic treatment for 30 minutes, filtering by using a 0.25-micron filter plug, injecting into an ink box, performing ink-jet printing in a working area of a working electrode at a printing interval of 20 microns, printing voltage of 36V, printing layers of 20 layers, printing height of 1000 microns, and drying and heating parameters of each layer at 50 ℃ for 15 minutes;
subsequently, the volume ratio of the PANI ink to the ethylene glycol is 1.2, ultrasonic treatment is carried out for 20 minutes, 0.8 ml of mixed solution is taken out, the mixed solution is filtered by a 0.25-micron filter plug and then is injected into an ink box, ink-jet printing is carried out on a working area of a working electrode, the printing interval is 20 microns, the printing voltage is 40 volts, the number of printing layers is 25, the printing height is 1000 microns, and the drying heating parameter of each layer is 50 ℃ for 15 minutes;
then FeCl 3 Ink for ink jet recordingThe volume ratio of the mixed solution to glycol is 1.26, ultrasonic treatment is carried out for 20 minutes, 0.8 ml of mixed solution is taken out, the mixed solution is filtered by a 0.25 micron filter plug and then injected into an ink box, ink-jet printing is carried out on a working area of a reference electrode, the printing interval is 20 microns, the printing voltage is 40 volts, the number of printing layers is 3, and the drying and heating parameters of each printing layer with the printing height of 1000 microns are 50 ℃ and 15 minutes;
finally, the volume ratio of the PVP ink to the hourly methanol was 1. Degree centigrade
Example 2
The pH sensor prepared in example 1 was tested:
the test was performed using the CHI 1000C electrochemical workstation, in which case the reference electrode was also the counter electrode. Therefore, the alligator clip of the counter electrode of the electrochemical workstation is required to be also connected on the reference electrode. The response voltages corresponding to the solutions with different pH values are measured by adopting an open circuit potential method (v-t test), the solutions with different pH values are prepared by citric acid and disodium phosphate solution, and the solutions are accurately calibrated by using a pH meter before use.
As shown in FIG. 5, the pH values tested were 4,5,6,7 from top to bottom, and the time to reach steady state voltage was observed to be less than 2 seconds, with a fast response speed.
FIG. 6 is a linear fit curve between different pH values and response voltages, showing that the prepared pH sensor has a linear R 2 At 0.9909, the sensitivity of the pH sensor was about 39 millivolts/pH.
FIG. 7 is a graph showing the selectivity test of a pH sensor in which the interfering substance contains 10 mM potassium chloride (KCl), 20 mM NaCl, and 1 mM ammonium chloride (NH) 4 Cl), all interfering solutions were prepared with phosphate buffered saline. As can be seen from fig. 7, the clear pH sensor has high selectivity, and shows superiority with substantially no change in voltage for interfering substances.
It will be understood that the invention is not limited to the examples described above, but that modifications and variations will occur to those skilled in the art in light of the above teachings, and that all such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.
Claims (12)
1. A method for preparing a flexible pH sensor by ink-jet printing is characterized by comprising the following steps:
providing Ag ink, au ink, PANI ink, feCl 3 Inks and PVB inks;
printing Ag ink on a flexible substrate at intervals by ink jet, and drying to obtain a working electrode and a reference electrode;
printing Au ink on the working electrode in an ink-jet manner, drying, then printing PANI ink in an ink-jet manner, and drying to obtain the working electrode based on Ag/Au/PANI;
ink-jet printing FeCl on the reference electrode 3 Ink, drying, then ink-jet printing PVB ink, drying to obtain the Ag/FeCl-based ink 3 PVB, namely preparing the flexible pH sensor.
2. The method for preparing a flexible pH sensor by ink-jet printing according to claim 1, wherein the preparation of the Au ink comprises the steps of:
PVP was added to HAuCl with continuous stirring 4 ·4H 2 Obtaining a first mixed solution in an O aqueous solution;
in NaBH 4 Adding an alkaline solution into the solution, stirring, and refrigerating and cooling to obtain a second mixed solution;
dropwise adding the second mixed solution into the first mixed solution, and reacting to obtain Au nanoparticles;
and adding the Au nano particles into a third mixed solution consisting of organic alcohol and deionized water, and performing ultrasonic redispersion to obtain the Au ink.
3. Method for manufacturing a flexible pH sensor according to the inkjet printing of claim 2, characterized in that the HAuCl 4 ·4H 2 The molar concentration of the O aqueous solution is 10-50 millimoles; the molar concentration of PVP is 10-50 millimole; the NaBH 4 The molar concentration of the solution is 1-5 mol, and the molar concentration of the NaOH solution is 1-5 mol.
4. The method of inkjet printing for making a flexible pH sensor according to claim 1, wherein the preparation of the PANI ink comprises the steps of:
mixing aniline solution and ammonium persulfate solution with equal volume under the condition of existence of hydrochloric acid, reacting to prepare PANI solution, and centrifuging the PANI solution to remove supernatant to prepare PANI nanowire;
and mixing the PANI nano-wire with deionized water, adding sodium dodecyl sulfate, and performing ultrasonic dispersion to obtain the PANI ink.
5. The method for preparing the flexible pH sensor by ink-jet printing according to claim 1, wherein in the ink-jet printing process, the ink-jet printing voltage is set to be 20-40 volts, and the ink-jet printing distance is 5-30 micrometers; the ink jet printing height is 500-2000 microns.
6. The method for preparing a flexible pH sensor by ink-jet printing according to claim 1, wherein the drying conditions for each printed layer during ink-jet printing are as follows: the temperature is 40-60 ℃ and the time is 0.2-0.6 h.
7. The method for preparing a flexible pH sensor by ink-jet printing according to claim 1, wherein before the Au ink is ink-jet printed on the working electrode, the Au ink is mixed with ethylene glycol according to a volume ratio of 1.2-1, so as to form a mixture with a viscosity of 8-12 centipoises and a density of 1.01-1.2kg/m 3 And Au printing liquid with the surface tension of 25-35 mN/m.
8. The method for preparing a flexible pH sensor by ink-jet printing according to claim 1, wherein before the PANI ink is ink-jet printed on the working electrode, the PANI ink is mixed with ethylene glycol according to a volume ratio of 1 to 0 to 1 to form a PANI printing solution with a viscosity of 8 to 12 centipoise, a density of 1.15 to 1.32kg/m3 and a surface tension of 30 to 44 mN/m.
9. Method for manufacturing a flexible pH sensor according to the ink-jet printing of claim 1, characterized in that FeCl is ink-jet printed on the reference electrode 3 FeCl is first added before ink 3 The ink is mixed with ethylene glycol according to a volume ratio of 1.1-1 3 FeCl with surface tension of 30-44mN/m 3 And (4) printing liquid.
10. The method for manufacturing a flexible pH sensor according to claim 1, wherein the PVB ink is mixed with glycerol in a volume ratio of 1 3 PVB printing liquid with surface tension of 68-80 mN/m.
11. The method of claim 1, wherein the Au ink, PANI ink, PVB ink and FeCl are printed in an inkjet process 3 The number of layers of the ink is 1-40.
12. A flexible pH sensor, characterized in that it is manufactured by the method of manufacturing a flexible glucose sensor according to any of claims 1-11.
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| MIGUEL ZEA 等: "Specially Designed Polyaniline/Polypyrrole Ink for a Fully Printed Highly Sensitive pH Microsensor", 《ACS APPLIED MATERIALS & INTERFACES》, pages 33524 - 33535 * |
| 钱君浩 编著: "《特种印刷新技术》", 中国轻工业出版社, pages: 12 * |
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