CN118047966A - Preparation method of graphene composite sensitive film for chloride ion electrochemical sensor - Google Patents
Preparation method of graphene composite sensitive film for chloride ion electrochemical sensor Download PDFInfo
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- CN118047966A CN118047966A CN202410201733.5A CN202410201733A CN118047966A CN 118047966 A CN118047966 A CN 118047966A CN 202410201733 A CN202410201733 A CN 202410201733A CN 118047966 A CN118047966 A CN 118047966A
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- sensitive film
- electrochemical sensor
- chloride ion
- preparation
- graphene composite
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims description 22
- 229910021389 graphene Inorganic materials 0.000 title claims description 22
- 239000002131 composite material Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- GYTDJCTUFWFXBE-UHFFFAOYSA-M (2,2,2-trifluoroacetyl)oxymercury Chemical compound [Hg+].[O-]C(=O)C(F)(F)F GYTDJCTUFWFXBE-UHFFFAOYSA-M 0.000 claims description 4
- CFPFMAGBHTVLCZ-UHFFFAOYSA-N (4-chlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(Cl)C=C1 CFPFMAGBHTVLCZ-UHFFFAOYSA-N 0.000 claims description 4
- CXVOIIMJZFREMM-UHFFFAOYSA-N 1-(2-nitrophenoxy)octane Chemical compound CCCCCCCCOC1=CC=CC=C1[N+]([O-])=O CXVOIIMJZFREMM-UHFFFAOYSA-N 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000012924 metal-organic framework composite Substances 0.000 claims description 4
- UOBBAWATEUXIQF-UHFFFAOYSA-N tetradodecylazanium Chemical compound CCCCCCCCCCCC[N+](CCCCCCCCCCCC)(CCCCCCCCCCCC)CCCCCCCCCCCC UOBBAWATEUXIQF-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 4
- 238000004140 cleaning Methods 0.000 abstract 2
- 238000002484 cyclic voltammetry Methods 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 2
- 238000009713 electroplating Methods 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- 244000137852 Petrea volubilis Species 0.000 abstract 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract 1
- 241001481789 Rupicapra Species 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000010985 leather Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000005498 polishing Methods 0.000 abstract 1
- 229910001414 potassium ion Inorganic materials 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 229910021642 ultra pure water Inorganic materials 0.000 abstract 1
- 239000012498 ultrapure water Substances 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention relates to the technical field of electrochemical sensor analysis, in particular to a preparation method of a PEDOT/nano silver K + selective electrode solid-state contact layer. The method is realized by the following steps: firstly, manually polishing by using sand paper and chamois leather, removing an oxide layer on the surface of a silver wire, and cleaning by using dilute hydrochloric acid and ultrapure water for 5 minutes for standby; a silver wire is connected to the cathode of the Schottky diode and is placed in a three-electrode electropolymerization system, and electroplating is carried out by a cyclic voltammetry deposition method; taking out the Schottky diode connected with the silver wire, and carrying out electroplating scanning for 5 circles in AgN0 3 and HCIO 4 acid salt mixed solution by using a cyclic voltammetry deposition method; repeating the steps four times, and cleaning and drying to obtain the solid-state contact layer of the solid-state potassium ion selective electrode. The preparation method is low in preparation cost and simple, and the prepared solid contact layer is matched with the sensitive film, so that the solid contact layer not only has equivalent sensitivity and selectivity, but also can develop towards the microelectrode.
Description
Technical Field
The invention relates to the field of preparation of composite sensitive electrochemical films, in particular to a preparation method of a graphene composite sensitive film for a chloride ion electrochemical sensor.
Background
Electrochemical sensors are a type of sensor device that performs qualitative and quantitative analysis and measurement, and converts chemical quantities of an object to be measured into electrical quantities for sensing and detection. At present, PVC and plasticizer are used as matrixes of the sensor membrane according to a certain proportion, and the characteristics of the PVC are represented by the free volume of chain segments and the movement characteristics of the chain segments. When the minimum free volume required for plasticizer molecule movement is less than the polymer segment free volume, the plasticizer molecule is able to diffuse through the polymer segment. The larger the free volume in PVC, the more likely the plasticizer molecules migrate. The graphene material is easy to disperse, has large specific surface area, provides more uniform and larger electroactive site distribution for high loading of electroactive substances and biomolecules, and the like, and has a layered framework structure which is easy to prepare a uniform and compact composite membrane, so that chain segment movement is effectively inhibited, and the performance of the membrane is improved. In addition, the pore canal of the graphene can also increase the mass transfer channel of the membrane so as to improve the flux of the membrane.
The graphene composite sensitive film with high loading capacity, uniformity, compactness and stability is prepared by using a natural pore-forming mode and is used for measuring the concentration of chloride ions.
Disclosure of Invention
Starting from the problem existing in the prior art, the invention aims to provide a preparation method of a graphene composite sensitive film for a chloride ion electrochemical sensor. The graphene composite sensitive film of the chloride ion electrochemical sensor provided by the invention shows good Nernst response to chloride ions.
The invention provides a preparation method of a graphene composite sensitive film for a chloride ion electrochemical sensor, which comprises the following steps:
1) The weight portions of the components are as follows:
2) Preparation:
S1, weighing polymer matrix material powder, a silane coupling agent, a cross-linking agent, graphene and dioctyl phthalate, adding into a flask with a plug, adding tetrahydrofuran, heating to 80 ℃, then reacting for 4 hours under magnetic stirring (rotating speed: 30 r/min), and standing at room temperature for 24 hours to obtain an S1 solution;
S2, adding quantitative 2-nitrophenyl octyl ether, tetra (dodecyl) ammonium tetra (4-chlorophenyl) borate and 4, 5-dimethyl-3, 6-dioctyl oxy-o-phenylene-bis (mercury trifluoroacetate) into the S1 solution completed in the step S1, stirring (the rotating speed is 30 r/min) for 60 minutes, and standing at room temperature for 24 hours to obtain an S2 solution; ;
S3, pouring the solution of the S2 into a clean glass sheet die, and standing for 48 hours at a dry room temperature to obtain the MOF composite sensitive film with the thickness of 0.7-1 mm.
The polymer matrix material powder in the step S1 is mixture powder of PVC-SG5 and PVC-SG 32 different brands of PVC.
The polymer powder in the step S1 is used in an amount of 35 to 65 parts by weight of PVC (SG 5).
The polymer powder in the step S1 is 65-35 parts of PVC (SG 3).
The total amount of PVC in the polymer powder described in step S1 is 100 parts.
The cross-linking agent in the step S1 is one or a mixture of two of epichlorohydrin and dodecyl mercaptan in any proportion.
The silane coupling agent in the step S1 is one or more of KH550, KH570 and KH592 mixed in any proportion.
The invention has at least the following beneficial effects:
The two-dimensional skeleton composite sensitive film for the chloride ion electrochemical sensor is provided, and the detection and analysis performances of the film are displayed. The graphene composite sensitive film suitable for the chloride ion electrochemical sensor has short recognition response time to chloride ions, can still keep good detection performance under the soaking of a solvent, and has good Nernst response and long-term potential stability. Meanwhile, the preparation method is simple, has short process flow, effectively improves the production efficiency and is beneficial to small-scale production.
The invention has great potential and market prospect in the fields of environmental monitoring, instant detection and the like.
Drawings
FIG. 1 is a potential change diagram of a graphene composite sensitive film for a chloride ion electrochemical sensor in a solution with a chloride ion concentration of 100-3000 mg/L.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The ion-selective electrodes prepared were all activated in 10 -1 M KCl solution for 24h before use.
The potential values in the experimental data are all corrected according to the Henderson formula, and the solution activity is corrected according to the Debye-Huckel formula.
Example 1
S1: 35mg of PVC (SG 5), 65mg of PVC (SG 3), 2mgKH mg of epoxy chloropropane, 5mg of graphene and 120mg of dioctyl phthalate are weighed and added into a flask with a plug, 3ml of tetrahydrofuran is added, the flask with the plug is heated to 80 ℃, then the reaction is carried out for 4 hours under the magnetic stirring (the rotating speed is 30 r/min), the beaker is sealed, and the beaker is placed at room temperature for 24 hours, wherein the solution name is S1;
S2: 120mg of 2-nitrophenyl octyl ether, 2mg of tetra (dodecyl) ammonium tetra (4-chlorophenyl) borate and 10mg of 4, 5-dimethyl-3, 6-dioctyloxy-o-phenylene-bis (mercury trifluoroacetate) are added into the S1 solution, stirring is completed for 30 minutes after sample addition, stirring is stopped, and a sample flask is placed at room temperature for 24 hours, wherein the solution name is S2;
S3: adjusting the level of the glass sheet mould; pouring the S2 solution on a clean glass sheet mould; s3-3: after 48 hours at dry room temperature, a film with a thickness of 0.5 to 1mm was obtained.
The MOF composite sensitive film constructed in the embodiment is applied to detection in an actual sample, and in a concentration interval of 50-2000 mg/L of chloride ions, the detected peak current has a good logarithmic linear relationship with the concentration, and R=0.9998. As shown in fig. 1.
Example 2
S1: 65mg of PVC (SG 5), 35mg of PVC (SG 3), 5mgKH792, 10mg of dodecyl mercaptan, 5mg of graphene and 120mg of dioctyl phthalate are weighed into a flask with a plug, 3ml of tetrahydrofuran is added, the flask with the plug is heated to 80 ℃, the reaction is carried out for 4 hours under magnetic stirring (rotating speed: 30 r/min), the beaker is sealed, and the solution is placed at room temperature for 24 hours, and is named S1.
S2: 120mg of 2-nitrophenyl octyl ether, 2mg of tetra (dodecyl) ammonium tetra (4-chlorophenyl) borate and 10mg of 4, 5-dimethyl-3, 6-dioctyloxy-o-phenylene-bis (mercury trifluoroacetate) are added into the S1 solution, stirring is completed for 30 minutes after sample addition, stirring is stopped, and a sample flask is placed at room temperature for 24 hours, wherein the solution name is S2;
S3: adjusting the level of the glass sheet mould, and pouring the S2 solution on the clean glass sheet mould; after 48 hours at dry room temperature, a film with a thickness of 0.7 to 1mm was obtained.
The MOF composite sensitive film constructed by the embodiment is applied to detection in an actual sample, and in a concentration interval of 50-2000 mg/L of chloride ions, the detected peak current has a good logarithmic linear relationship with the concentration, and R= 0.9996.
Claims (7)
1. A preparation method of a graphene composite sensitive film for a chloride ion electrochemical sensor is characterized by comprising the following steps of:
1) The weight portions of the components are as follows:
2) Preparation:
S1, weighing polymer matrix material powder, a silane coupling agent, a cross-linking agent, graphene and dioctyl phthalate, adding into a flask with a plug, adding a proper amount of tetrahydrofuran, heating to 80 ℃, magnetically stirring at a rotating speed of 30r/min for 4 hours for reaction, and standing at room temperature for 24 hours to obtain an S1 solution;
s2, adding quantitative 2-nitrophenyl octyl ether, tetra (dodecyl) ammonium tetra (4-chlorophenyl) borate and 4, 5-dimethyl-3, 6-dioctyl-oxy-o-phenylene-bis (mercury trifluoroacetate) into the S1 solution completed in the step S1, reacting for 60 minutes under stirring at the rotating speed of 30r/min, and standing at room temperature for 24 hours;
S3, pouring the S2 solution into a clean glass sheet die, and standing for 48 hours at a dry room temperature to obtain the MOF composite sensitive film with the thickness of 0.7-1 mm.
2. The preparation method of the graphene composite sensitive film for the chloride ion electrochemical sensor, which is disclosed in claim 1, is characterized in that the polymer matrix material powder in the step S1 is mixture powder of PVC-SG5 and PVC-SG3 with two different brands.
3. The method for preparing the graphene composite sensitive film for the chloride ion electrochemical sensor according to claim 1, wherein the polymer powder in the step S1 is 35-65 parts of PVC-SG 5.
4. The method for preparing the graphene composite sensitive film for the chloride ion electrochemical sensor according to claim 1, wherein the polymer powder in the step S1 is 65-35 parts of PVC-SG 3.
5. The method for preparing the graphene composite sensitive film for the chloride ion electrochemical sensor according to claim 1, wherein the total amount of the polymer powder and the PVC in the step S1 is 100 parts.
6. The method for preparing the graphene composite sensitive film for the chloride ion electrochemical sensor according to claim 1, wherein the cross-linking agent in the step S1 is one or a mixture of two of epichlorohydrin and dodecyl mercaptan in any proportion.
7. The preparation method of the graphene composite sensitive film for the chloride ion electrochemical sensor, which is disclosed in claim 1, is characterized in that the silane coupling agent in the step S1 is one or a mixture of more than one of KH550, KH570 and KH592 in any proportion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410201733.5A CN118047966A (en) | 2024-02-23 | 2024-02-23 | Preparation method of graphene composite sensitive film for chloride ion electrochemical sensor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410201733.5A CN118047966A (en) | 2024-02-23 | 2024-02-23 | Preparation method of graphene composite sensitive film for chloride ion electrochemical sensor |
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| CN118047966A true CN118047966A (en) | 2024-05-17 |
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