CN116731319A - Perylene bisimide covalent organic polymer film and preparation method and application thereof - Google Patents
Perylene bisimide covalent organic polymer film and preparation method and application thereof Download PDFInfo
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- CN116731319A CN116731319A CN202310711488.8A CN202310711488A CN116731319A CN 116731319 A CN116731319 A CN 116731319A CN 202310711488 A CN202310711488 A CN 202310711488A CN 116731319 A CN116731319 A CN 116731319A
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- trimethylamine
- covalent organic
- organic polymer
- polymer film
- perylene bisimide
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 27
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000004044 response Effects 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 8
- -1 THSTZ Chemical compound 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 claims description 3
- ZBOLYDUBEGGDKS-UHFFFAOYSA-N 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=C(Cl)C=C(C(O)=O)C2=C(C(O)=O)C=C(Cl)C=1C1=C(Cl)C=C(C(O)=O)C2=C1C3=C(Cl)C=C2C(=O)O ZBOLYDUBEGGDKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000004043 responsiveness Effects 0.000 abstract description 2
- 238000012697 Liquid/Liquid Interfacial Polymerization Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 34
- 239000010408 film Substances 0.000 description 31
- 239000011521 glass Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000014102 seafood Nutrition 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010015946 Eye irritation Diseases 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000013 eye irritation Toxicity 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002685 pulmonary effect Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a perylene bisimide covalent organic polymer film material and a preparation method thereof, and also relates to application of the organic polymer film in trimethylamine gas sensitivity. The invention provides a liquid-liquid interfacial polymerization method for preparing a covalent organic polymer film, and transferring the film to an ITO interdigital electrode to prepare a trimethylamine gas sensor. The sensor with excellent gas sensitivity has the advantages of good responsiveness, high sensitivity, quick response and recovery time, good reproducibility and strong selectivity to trimethylamine with different concentrations; and the preparation is simple, the production cost is low, the environment is protected, and the method can be used for detecting the trimethylamine with low concentration in the environment.
Description
Technical Field
The invention relates to the technical field of preparation and application of composite material interface reaction, in particular to a preparation method of a perylene bisimide covalent organic polymer film material (PDI-COP) and application of trimethylamine detection.
Background
Trimethylamine (TMA) is a Volatile Organic Compound (VOC), a colorless liquefied gas, and has an ammonia odor of fishy smell. Is soluble in water, ethanol and diethyl ether. Is easy to burn. TMA is very harmful to human health, such as eye irritation, headache, dyspnea, pulmonary infection, and even death. Trimethylamine can be secreted in microorganisms containing nitrogen oxides generated in the process of deteriorating dead fish and marine organisms, and the concentration and the proportion of the trimethylamine can be used as effective indexes for evaluating the freshness of fish and seafood. Today, in order to ensure that the quality of fish and seafood products during cold chain transport meets consumer requirements, it is of great value to monitor and predict the quality of fish and seafood products during transport and storage in real time.
At present, the trimethylamine gas in the environmental field is usually detected by using a gel chromatography technology, an electrochemical analysis method, a colorimetry method and other methods, but the defects of large volume, high price, incapability of real-time detection and the like limit the application of the trimethylamine gas in the actual life. Meanwhile, various metal oxide semiconductor-based chemical resistance type gas sensors generally require high operating temperatures, which limits their practical application. Ambient humidity is also a challenge for metal oxide gas sensors, which can produce false responses, producing unreliable results.
Disclosure of Invention
The invention aims to provide a preparation method of a perylene imide group covalent organic polymer film material for detecting trimethylamine, which is characterized by comprising the following steps:
(1) 1,6,7, 12-tetrachloro-3, 4,9, 10-perylene tetracarboxylic dianhydride (PTCDA) was dissolved in chloroform as the lower organic layer, and then pure water was slowly added to the upper surface of the solution, leaving a stable chloroform/water interface. Subsequently, trihydrazinotriazine (THSTZ) and p-toluene sulfonic acid (PTSA) were dissolved in dimethyl sulfoxide as the upper organic layer and slowly added to the beaker. Reaction 36-72 h at room temperature, wherein the mass ratio of PTCDA, THSTZ, PTSA is 5:1.1-1.6:0.1-0.3, the volume ratio of the chloroform, the dimethyl sulfoxide and the deionized water is 1:0.3-0.5:1-1.2, volume of 125-145 mL;
(2) After the reaction is finished, the film is washed by deionized water for a plurality of times, and a pale yellow smooth film is clearly observed at the interface of two phases, namely the perylene bisimide covalent organic polymer film material.
Wherein, the perylene bisimide covalent organic polymer film, PDI-COP for short, has a structural formula shown in formula 1;
1 (1)
The application of the perylene bisimide covalent organic polymer film material in preparing trimethylamine gas sensor.
A gas sensor for detecting trimethylamine comprises an ITO conductive glass substrate, wherein the ITO conductive glass substrate is etched into ITO interdigital electrodes, and perylene imide group covalent organic polymer films PDI-COP are arranged on the surfaces of the ITO interdigital electrodes.
The preparation method for constructing the gas sensor for detecting trimethylamine comprises the following steps:
(1) Preparation of ITO conductive glass interdigital electrode: taking ITO conductive glass, cleaning, drying, and etching an ITO conductive glass substrate into ITO interdigital electrodes (in the prior art);
the ITO interdigital electrode treatment method comprises the following specific steps: placing the ITO interdigital electrodes into a beaker, respectively ultrasonically cleaning with solvents of different polarities, namely toluene, acetone, absolute ethyl alcohol and distilled water, each solvent being cleaned for three times, five minutes each time, and then vacuum drying for later use;
(2) Transferring the PDI-COP film at the interface to a transparent conductive film (ITO) interdigital electrode with a glass substrate, wherein the number of transfer film layers is 1-4, and drying in vacuum after the solvent volatilizes to obtain the gas sensor.
The gas sensor for measuring trimethylamine prepared by the invention comprises the covalent organic polymer film PDI-COP constructed by perylene dianhydride compound PTCDA and triazine compound THSTZ, and the covalent organic polymer film PDI-COP has the advantages of good responsiveness, high sensitivity, quick response and recovery time, good reproducibility and strong selectivity to trimethylamine in the range of 150-12 ppm at room temperature, and the covalent organic polymer film shows excellent gas-sensitive performance.
The invention has the advantages that:
(1) The nano material for detecting trimethylamine has the advantages of simple preparation method and relatively low energy consumption;
(2) The gas sensor for detecting trimethylamine has the advantages of being capable of effectively and rapidly detecting the trimethylamine at room temperature
Trimethylamine, and no potential safety hazard; the response concentration to harmful gas trimethylamine is as low as 4 ppm, the response and recovery time is quick, the stability is good, the anti-interference performance is strong, and the selectivity is good; simple structure and preparation process, low cost and convenient industrialization.
Drawings
FIG. 1 is a cross-sectional view of a scanning electron microscope of PDI-COP;
FIG. 2 is a Fourier infrared spectrum of PDI-COP;
FIG. 3 is an X-ray diffraction (XPS) spectrum of PDI-COP;
FIG. 4 is a long-term stability curve (room temperature conditions) of trimethylamine gas sensor against 80 ppm trimethylamine over 30 days;
FIG. 5 is a response/recovery time curve (room temperature condition) of a trimethylamine gas sensor of 80 ppm trimethylamine;
FIG. 6 is a trimethylamine gas sensor reproducibility test curve (room temperature condition);
FIG. 7 is a response-time curve (room temperature condition) of trimethylamine gas sensor to trimethylamine at different concentrations;
FIG. 8 is a schematic diagram of the selectivity of trimethylamine gas sensor to different gases.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the present invention, but the content of the present invention is not limited to the following embodiments, and various details in the present specification may be modified or changed in various ways based on different points of view and applications without departing from the spirit of the present invention.
It should be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments and is not intended to limit the scope of the invention in which the specific conditions are not indicated in the following examples, typically in accordance with conventional conditions or in accordance with the conditions recommended by the respective manufacturer.
When numerical ranges are given in the examples, it is to be understood that unless otherwise indicated, the two endpoints of each numerical range and any numerical value between the two endpoints are optional, unless otherwise defined, that all technical and scientific terms used herein and those skilled in the art to which this invention pertains are aware and the description of this invention, and that any method, apparatus, and material of the prior art similar or equivalent to the method, apparatus, material described in the examples of this invention may be used to practice this invention.
EXAMPLE 1 preparation method of perylene bisimide covalent organic Polymer film PDI-COP
1.1
(1) 0.02 g of PTCDA was dissolved in 50 mL chloroform as the lower organic layer, and then 40 ml pure water was slowly added to the upper surface of the solution, leaving a stable chloroform/water interface. Subsequently, 0.0044 g THSTZ and 0.0004 g PTSA were dissolved in 15 mL dimethyl sulfoxide and 20 mL deionized water as the upper organic layer and slowly added to the beaker. The interface reaction of 36 h was performed at room temperature. After the reaction is finished, deionized water is used for cleaning for a plurality of times, and a pale yellow smooth film layer is clearly observed at the interface of two phases, namely PDI-COP;
(2) The obtained product is fully characterized, and FIG. 1 is a scanning electron microscope cross-sectional image of a perylene bisimide covalent organic polymer film material, showing the surface morphology and thickness of the film material. As shown in FIG. 2, the Fourier transform infrared spectrum shows a spectrum of the material at 1736-1738 cm compared to the original material -1 At the anhydride peak and 3426 cm -1 The amino peak disappears and in perylene imide covalent organic polymer film materials is also shown in 1322 and 1322 cm -1 A new characteristic peak of PDI-COP was found, which indicates successful synthesis of PDI-COP. As shown in FIG. 3, the XPS measurement spectrogram shows that C, N, O, cl elements coexist in the perylene bisimide covalent organic polymer film material structure
1.2
(1) 0.02 g of PTCDA was dissolved in 50 mL chloroform as the lower organic layer, and then 40 ml pure water was slowly added to the upper surface of the solution, leaving a stable chloroform/water interface. Subsequently, 0.0052 g THSTZ and 0.0008 g PTSA were dissolved in 20 mL dimethyl sulfoxide and 25 mL deionized water as the upper organic layer and slowly added to the beaker. The interfacial reaction of 54 h was performed at room temperature. After the reaction is finished, deionized water is used for cleaning for a plurality of times, and a pale yellow smooth film layer is clearly observed at the interface of two phases, namely PDI-COP;
(2) The film product obtained was characterized in its entirety: the results are consistent with 1.1
1.3
(1) 0.02 g of 1,6,7, 12-tetrachloro-3, 4,9, 10-perylenetetracarboxylic dianhydride (PTCDA) was dissolved in 50 mL chloroform as the lower organic layer, and then 40 ml pure water was slowly added to the upper surface of the solution, leaving a stable chloroform/water interface. Subsequently, 0.0064 g trihydrazinotriazine and 0.0012 g p-toluene sulfonic acid were dissolved in 25 mL dimethyl sulfoxide and 30 mL deionized water as the upper organic layer and slowly added to the beaker. The interface reaction of 72 h was performed at room temperature. After the reaction is finished, deionized water is used for cleaning for a plurality of times, and a pale yellow smooth film layer is clearly observed at the interface of two phases, namely PDI-COP;
(2) The film product obtained was characterized in its entirety: the results are consistent with 1.1.
Example 2 preparation of gas sensor for trimethylamine
(1) Preparation of ITO conductive glass interdigital electrode: taking ITO conductive glass, cleaning, drying, and etching an ITO conductive glass substrate into ITO interdigital electrodes (in the prior art);
(2) The ITO interdigital electrode treatment method comprises the following specific steps: placing the ITO interdigital electrodes into a beaker, respectively ultrasonically cleaning with solvents of different polarities, namely toluene, acetone, absolute ethyl alcohol and distilled water, each solvent being cleaned for three times, five minutes each time, and then vacuum drying for later use;
(3) And transferring the PDI-COP film at the interface to an interdigital electrode with (ITO), wherein the number of the transferred film layers is 2, and drying in vacuum after the solvent volatilizes to obtain the gas sensor.
Example 3 Performance test of trimethylamine gas sensor
The covalent organic polymer film PDI-COP obtained in example 2 was selected to construct a gas-sensitive test device, and a gas-sensitive test experiment was performed. The gas sensitive test procedure is a gas sensitive performance performed in a relatively mild environment (room temperature, ambient atmospheric pressure and dry air) and a fixed bias voltage of 5V between the two electrodes. Using a test instrument: agilent B290a precision source/measurement unit. The gas sensors prepared by adopting the covalent organic polymer film PDI-COP prepared in the embodiment 2 are respectively tested, and the test results are consistent; as shown in fig. 4-8. As shown in fig. 5, the response/recovery times are 96 s and 64 s, respectively; as shown in fig. 4 and 6, the long-term stability of the covalent organic polymer film PDI-COP gas sensor in 30 days is basically consistent with the repeated stability of 80 ppm trimethylamine, which indicates that the stability of the gas sensor is very good; as shown in FIG. 7, the covalent organic polymer film PDI-COP gas sensor has good response to 150-12 ppm trimethylamine, and the detection limit can reach 4 ppm; as shown in fig. 8, the covalent organic polymer thin film PDI-COP gas sensor was subjected to gas-sensitive test for 100 ppm of different gases including trimethylamine, triethylamine, methanol, ethanol, acetone, acetic acid, ammonia, carbon monoxide and nitric oxide, and it can be seen that the covalent organic polymer thin film PDI-COP showed the greatest response to trimethylamine and good selectivity to trimethylamine among various test gases.
The above embodiments are merely illustrative of the principles and functions of the present invention, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims of this invention, which are within the skill of those skilled in the art, can be made without departing from the spirit and scope of the invention disclosed herein.
Claims (7)
1. A perylene bisimide based covalent organic polymer film material (PDI-COP) having the structural formula shown in figure 1:
FIG. 1.
2. A perylene bisimide covalent organic polymer film material PDI-COP, which is structurally characterized by having a wrinkled film structure with an average thickness of 30 nm.
3. The preparation method of the perylene bisimide covalent organic polymer film material PDI-COP is characterized by comprising the following steps:
(1) 1,6,7, 12-tetrachloro-3, 4,9, 10-perylenetetracarboxylic dianhydride (PTCDA) was dissolved in chloroform as the lower organic layer, then pure water was slowly added to the upper surface of the solution, leaving a stable chloroform/water interface, and then trihydrazinotriazine (THSTZ) and p-toluenesulfonic acid (PTSA) were dissolved in dimethyl sulfoxide as the upper organic layer and slowly added to a beaker, and reacted at room temperature 36-72 h, wherein PTCDA, THSTZ, PTSA has a mass ratio of 5:1.1-1.6:0.1-0.3, total mass 24.8-27.6 mg; the volume ratio of the chloroform to the dimethyl sulfoxide to the pure water is 1:0.3-0.5:1.2-1.4, and the total volume is 125-145 mL;
(2) After the reaction is completed, the reaction product is washed by deionized water for a plurality of times, and a pale yellow smooth film is clearly observed at the interface of the two phases, namely the PDI-COP.
4. Use of a perylene bisimide-based covalent organic polymeric film according to claim 2, characterized in that: detection of trimethylamine gas at room temperature.
5. Use of a perylene bisimide-based covalent organic polymeric film according to claim 2, characterized in that: in the concentration range of 150-12 ppm, the response current gradually increases with the increase of the trimethylamine concentration, and the trimethylamine concentration and the current response are in a linear relation.
6. Use of a perylene bisimide-based covalent organic polymeric film according to claim 2, characterized in that: the limit of detection of trimethylamine was 4 ppm.
7. Use of a perylene bisimide-based covalent organic polymeric film according to claim 2, characterized in that: response and recovery times to trimethylamine were 96 s and 63 s, respectively.
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| CN102353661A (en) * | 2011-06-29 | 2012-02-15 | 陕西师范大学 | Fluorescent sensor film preparation method based on perylene diimide cholesterol derivative |
| CN102702546A (en) * | 2012-05-10 | 2012-10-03 | 陕西师范大学 | Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof |
| CN109467568A (en) * | 2018-11-08 | 2019-03-15 | 济南大学 | A kind of porphyrin naphthalene cyanines three-layer metal complex and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353661A (en) * | 2011-06-29 | 2012-02-15 | 陕西师范大学 | Fluorescent sensor film preparation method based on perylene diimide cholesterol derivative |
| CN102702546A (en) * | 2012-05-10 | 2012-10-03 | 陕西师范大学 | Preparation method of perylene bisimide cholesterol polymer gel fluorescent sensing film, and application thereof |
| CN109467568A (en) * | 2018-11-08 | 2019-03-15 | 济南大学 | A kind of porphyrin naphthalene cyanines three-layer metal complex and its preparation method and application |
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