CN109828002B - Nitrogen dioxide gas sensitive material based on tetrapyryl porphyrin cobalt aggregate - Google Patents
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 18
- 239000010941 cobalt Substances 0.000 title claims abstract description 18
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- OUDXAAXXNFMVGY-UHFFFAOYSA-N [O--].[Zn++].c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3 Chemical class [O--].[Zn++].c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3 OUDXAAXXNFMVGY-UHFFFAOYSA-N 0.000 description 1
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- QCAZZPKUBLATEK-UHFFFAOYSA-L cobalt(2+) diacetate dihydrate Chemical compound O.O.[Co+2].CC([O-])=O.CC([O-])=O QCAZZPKUBLATEK-UHFFFAOYSA-L 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of nitrogen dioxide room temperature detection research, in particular to preparation and application of a tetrapyryl porphyrin cobalt aggregate gas sensitive material. Introducing four pyrenyl groups into four meso-positions of porphyrin to obtain a 5,10,15, 20-tetra (1-pyrenyl) cobalt porphyrin compound, and adding 2.5mL of methanol into 0.5mL of 1 × 10 by utilizing the characteristic that the cobalt tetrapyrenyl porphyrin compound has obvious solubility difference in dichloromethane and methanol‑3In a dichloromethane solution of the tetrapyryl porphyrin cobalt in mol/L, self-assembled aggregates are separated out; the generated self-assembly aggregate is dripped on a glass substrate with an ITO interdigital electrode to be used as a semiconductor active layer, so that the low-concentration NO can be treated in the range of 0-75% of humidity at room temperature2Sensitive and rapid detection, and the detection limit is 50 ppb.
Description
Technical Field
The invention relates to the field of nitrogen dioxide room temperature detection research, in particular to preparation and application of a tetrapyryl porphyrin cobalt aggregate gas sensitive material. Introducing four pyrenyl groups into four meso-positions of porphyrin to obtain a 5,10,15, 20-tetra (1-pyrenyl) cobalt porphyrin compound, and adding 2.5mL of methanol into 0.5mL of 1 × 10-3In a dichloromethane solution of the tetrapyryl porphyrin cobalt in mol/L, self-assembled aggregates are separated out; the generated self-assembly aggregate is dripped on a glass substrate with an ITO interdigital electrode to be used as a semiconductor active layer, so that the low-concentration NO can be treated in the range of 0-75% of humidity at room temperature2Sensitive and rapid detection, and the detection limit is 50 ppb. The introduction of four pyrenyl groups enlarges the conjugation degree of porphyrin, accelerates the flow of electrons, is favorable for sensitive response of devices, in addition, the cobalt tetrapyryl porphyrin aggregate prepared by the method has a unique 'pinecone' shape formed by splicing and inserting sheet-shaped blades, and a channel and a large specific surface area brought by the special 'splicing and inserting' structure are high-sensitivity detection of low-concentration NO under high humidity2Providing the possibility.
Background
With the growing concern of people on environment and health, the development of new low-cost and high-performance gas sensing materials and devices for monitoring toxic and harmful gases in the environment has become a field of preferential development. Porphyrins are a class of natural macrocyclic compounds, are closely related to life phenomena, and widely exist in nature. Due to the large planar macrocyclic conjugated molecular structure of porphyrin, high chemical stability and the modifiability of the molecular structure, the porphyrin derivative has been widely researched and applied in the fields of biochemistry, photoelectrocatalysis, gas sensing and the like. However, the poor conductivity of porphyrin molecules causes the prepared gas sensor to have the defects of low responsiveness, low sensitivity, poor selectivity and the like, and limits further application of the gas sensor. Therefore, there is an increasing research choice to compound porphyrins with other materials to further improve gas sensing properties. For example, Mosciano et al prepared zinc oxide-porphyrin derivatives and found that the sensitivity based on this complex was superior to that of single porphyrin and reached 39% ppm for CO gas-1 (21％m3·mg-1) (Procedia eng.,2015,120: 71-74). Shirsat et al used single-walled carbon nanotubes in combination with tetraphenylporphyrin to produce a nanosensor array with excellent gas selectivity, overcoming the problem of poor gas sensor selectivity (J. Phys. chem. C., 2012,116: 3845-3850).
However, in some high humidity places, the stability and sensitivity of the sensing device are inevitably affected by humidity, so that the real gas concentration cannot be reflected, and Guang et al obtains an ordered aggregation structure from sandwich type rare earth phthalocyanine porphyrin by a phase transfer method, and uses the ordered aggregation structure for bipolar OFET devices (ACS applied materials)&INTERFACES,2016,8.9:6174-6182), therefore, the invention adopts the phase transfer method to prepare the room temperature NO detection with low cost, high sensitivity and quick response under high humidity2The gas sensitive material is a cobalt tetrapyrenyl porphyrin aggregate.
Disclosure of Invention
The invention relates to the field of nitrogen dioxide room temperature detection research, in particular to preparation and application of a tetrapyryl porphyrin cobalt aggregate gas sensitive material. Introducing four pyrene groupsAdding into four meso-positions of porphyrin to obtain 5,10,15, 20-tetra (1-pyrenyl) cobalt porphyrin compound, and adding 2.5mL of methanol into 0.5mL of 1 × 10-3In a dichloromethane solution of the tetrapyryl porphyrin cobalt in mol/L, self-assembled aggregates are separated out; the generated self-assembly aggregate is dripped on a glass substrate with an ITO interdigital electrode to be used as a semiconductor active layer, so that the low-concentration NO can be treated in the range of 0-75% of humidity at room temperature2Sensitive and rapid detection, and the detection limit is 50 ppb. The introduction of four pyrenyl groups enlarges the conjugation degree of porphyrin, accelerates the flow of electrons, is favorable for sensitive response of the device, in addition, the tetrapyryl porphyrin cobalt gas sensitive device prepared by the method has unique 'pinecone' shape formed by splicing and inserting sheet-shaped blades, and the channel and large specific surface area brought by the special 'splicing and inserting' structure are high-sensitivity NO detection with low concentration under high humidity2Providing the possibility.
The molecular structure of the cobalt tetrapyryl porphyrin is shown as follows:
synthesis of cobalt tetrapyryl porphyrin:
step 1: taking 100mg of tetrapyranyl free porphyrin and 80mg of cobalt acetate dihydrate into a 100ml three-neck flask, and adding 9ml of trichloromethane and 1ml of methanol;
step 2: heating to 63 ℃, stirring and refluxing for six hours, stopping heating, and cooling to room temperature;
and step 3: allowing chloroform/petroleum ether (volume ratio of 1:1) to pass through the column, wherein the first zone is a product zone, and performing rotary evaporation and evaporation to dryness;
and 4, step 4: recrystallizing with dichloromethane/methanol (volume ratio of 1:5), filtering, collecting brick red precipitate on filter paper, and drying for 6 hours at 40 ℃ in vacuum to obtain the cobalt tetrapyrylporphyrin (CoTPyP) with the yield of 22%.
The preparation method of the nitrogen dioxide gas sensitive material with the specific morphology of the cobalt tetrapyrylporphyrin aggregate comprises the following steps:
step 1: carrying out ultrasonic treatment on the ITO conductive glass for 15 minutes by using deionized water, ethanol and dichloromethane respectively, and then carrying out plasma cleaning for 10 minutes;
step 2: adding 2.5mL of methanol solvent into 0.5mL of a dichloromethane solution of tetrapyrylporphyrin cobalt, standing for 12h, and realizing induced precipitation and self-assembly of the nano structure at room temperature;
and step 3: and dripping the prepared self-assembly suspension onto an ITO conductive glass sheet, and standing and aging at 35 ℃ for 1 hour to obtain the gas sensitive device with a specific morphology.
Wherein the methanol is a poor solvent of the cobalt tetrapyrylporphyrin.
Wherein dichloromethane is a good solvent for cobalt tetrapyrylporphyrin.
Wherein only the cobalt-added tetrapyrene substituted porphyrin self-assembly can form the shape of a pinecone by a phase transfer method
Wherein the dropping amount of the self-assembly is 1-2 drops.
The invention has the beneficial effects that: a gas-sensitive device with a specific hydrophobic morphology is synthesized by using a phase transfer method. The gas sensitive device has simple preparation process and equipment, mild preparation conditions and easy realization of industrial production. Porphyrin substituted by pyrene-containing organic matter can effectively enlarge the conjugation degree of porphyrin, namely, the electron transfer capability is improved. The conductivity, sensitivity and hydrophobicity of the gas sensitive device constructed by the method are obviously increased, and the ratio of a good solvent to a poor solvent is controlled by adopting a phase transfer method and utilizing the interaction between the cobalt molecules of the tetrapyrylporphyrin and the obvious difference between the cobalt molecules of the tetrapyrylporphyrin in the good solvent and the poor solvent, so that the controllable synthesis of the appearance of the assembly with the 'splicing and inserting' structure is realized.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a mass spectrum of cobalt tetrapyrylporphyrin;
FIG. 2 is a nuclear magnetic map of cobalt tetrapyrylporphyrin;
FIG. 3 is a diagram of the ultraviolet-visible absorption spectrum of cobalt tetrapyryl porphyrin, wherein 1 is a diagram of the ultraviolet-visible absorption spectrum of cobalt tetrapyryl porphyrin in a dichloromethane solution, and 2 is a diagram of the ultraviolet-visible absorption spectrum of a cobalt tetrapyryl porphyrin assembly;
fig. 4 is an SEM image of a tetrapyrenyl porphyrin cobalt assembly;
FIG. 5 is an I-V curve of a cobalt tetrapyrylporphyrin assembly at different humidities, with 0% humidity 1, 45% humidity 2 and 75% humidity 3;
FIG. 6 is a graph showing the gas sensitivity test of a cobalt tetrapyrylporphyrin assembly to nitrogen dioxide under different humidity conditions, wherein 1 humidity is 0%, 2 humidity is 45%, 3 humidity is 75%, and 4 is the sensitivity graph under different humidity conditions, and it can be seen that cobalt tetrapyrylporphyrin has higher sensitivity and humidity resistance than porphyrin without cobalt, even if the humidity is up to 75%, the lowest detection limit of cobalt-substituted porphyrin reaches 50ppb, and the sensitivity reaches 257% ppm-1。
Detailed Description
Example 1: the method comprises the following steps of taking cobalt tetrapyrylporphyrin as an organic semiconductor material, and detecting nitrogen dioxide gas under a dry condition by using the cobalt tetrapyrylporphyrin. Firstly, sucking and dripping 1-2 assembled cobalt tetrapyryl porphyrin on ITO conductive glass by using a dropper, and heating for 1 hour at 35 ℃ on a heating table to ensure that the solution is fully volatilized. And then carrying out gas-sensitive test on the ITO conductive glass with the cobalt tetrapyrylporphyrin on a Keysight B2912A instrument to finally obtain the detection condition of the cobalt tetrapyrylporphyrin on nitrogen dioxide gas under a dry condition.
Example 2: the method is characterized in that cobalt tetrapyrylporphyrin is used as an organic semiconductor material, and nitrogen dioxide gas under a humidity condition is detected by using the cobalt tetrapyrylporphyrin. Firstly, sucking and dripping 1-2 assembled cobalt tetrapyryl porphyrin on ITO conductive glass by using a dropper, and heating for 1 hour at 35 ℃ on a heating table to ensure that the solution is fully volatilized. And then carrying out gas sensitivity test on the ITO conductive glass with the cobalt tetrapyryl porphyrin on a Keysight B2912A instrument, and passing nitrogen passing through the ITO conductive glass through a sodium chloride solution with a certain concentration to control the humidity of the nitrogen to be 0%, so that the detection sensitivity of the cobalt tetrapyryl porphyrin to nitrogen dioxide gas under the condition that the humidity is 0% reaches 44.7%, and the lowest detection limit is 50 ppb.
Example 3: the method is characterized in that cobalt tetrapyrylporphyrin is used as an organic semiconductor material, and nitrogen dioxide gas under a humidity condition is detected by using the cobalt tetrapyrylporphyrin. Firstly, sucking and dripping 1-2 assembled cobalt tetrapyryl porphyrin on ITO conductive glass by using a dropper, and heating for 1 hour at 35 ℃ on a heating table to ensure that the solution is fully volatilized. And then carrying out gas sensitivity test on the ITO conductive glass with the cobalt tetrapyryl porphyrin on a Keysight B2912A instrument, and passing nitrogen passing through the ITO conductive glass through a sodium chloride solution with a certain concentration to control the humidity of the nitrogen to be 45%, so that the detection sensitivity of the cobalt tetrapyryl porphyrin to nitrogen dioxide gas under the condition that the humidity is 45% reaches 92.9%, and the lowest detection limit is 50 ppb.
Example 4: the method is characterized in that cobalt tetrapyrylporphyrin is used as an organic semiconductor material, and nitrogen dioxide gas under a humidity condition is detected by using the cobalt tetrapyrylporphyrin. Firstly, sucking and dripping 1-2 assembled cobalt tetrapyryl porphyrin on ITO conductive glass by using a dropper, and heating for 1 hour at 35 ℃ on a heating table to ensure that the solution is fully volatilized. And then carrying out gas sensitivity test on the ITO conductive glass with the cobalt tetrapyryl porphyrin on a Keysight B2912A instrument, and passing nitrogen passing through the ITO conductive glass through a sodium chloride solution with a certain concentration to control the humidity of the nitrogen to be 75%, so that the detection sensitivity of the cobalt tetrapyryl porphyrin to nitrogen dioxide gas under the condition that the humidity is 75% reaches 257% and the lowest detection limit is 50 ppb.
The tetrapyryl cobalt porphyrin synthesized by the method can be obtained by synthesizing porphyrin through an original propionic acid method, so that the process flow is greatly simplified, the preparation condition is mild, the cost is low, the required equipment is simple, the production safety is high, and the industrial production is easy to realize. The synthesized cobalt tetrapyrylporphyrin can detect nitrogen dioxide gas under a dry condition, can improve the detection sensitivity of nitrogen dioxide under high humidity, and improves the application range of the gas sensor.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention can be smoothly implemented by those skilled in the art in the light of the accompanying drawings and the above description; however, those skilled in the art should, upon attaining an understanding of the present disclosure, appreciate that many changes, modifications, and equivalents may be made to the invention without departing from the spirit and scope of the invention; meanwhile, any changes, modifications, evolutions, etc. of the equivalent changes made to the above embodiments according to the implementation technology of the present invention are within the protection scope of the technical solution of the present invention.
Claims (3)
1. A gas sensitive material based on a tetrapyryl porphyrin cobalt aggregate is a 5,10,15, 20-tetra (1-pyrenyl) porphyrin cobalt aggregate, and nitrogen dioxide gas with the concentration as low as ppb level is detected in the humidity range of 0% -75%; the method is characterized in that 2.5mL of methanol is added to 0.5mL of 1 × 10 by utilizing the characteristic that the cobalt tetrapyrylporphyrin compound has obvious difference in solubility in a dichloromethane solvent and a methanol solvent-3Standing the upper layer of a dichloromethane solution of the tetrapyryl porphyrin cobalt in mol/L at room temperature for 12 hours, and separating out a self-assembled aggregate; the generated self-assembly aggregate is dripped on a glass substrate with an ITO interdigital electrode to be used as a semiconductor active layer, so that NO can be treated in a wide humidity range at room temperature2Sensitive and quick response.
2. The gas sensitive material based on the tetrapyryl porphyrin cobalt aggregates as recited in claim 1, wherein a drop tube is used to drop a suspension of the self-assembled aggregates onto the surface of the ITO interdigital electrode, and the electrode area is 24.6mm2The volume of the dropwise addition is 1-2 drops, and the semiconductor active layer on the electrode is aged for 1 hour at 35 ℃.
3. The gas-sensitive material based on the tetrapyryl porphyrin cobalt aggregates of claim 1, wherein nitrogen dioxide gas is detected under room temperature conditions in a humidity range of 0% to 75% with a minimum detection limit of 50 ppb.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102687001A (en) * | 2010-08-05 | 2012-09-19 | 松下电器产业株式会社 | Sensing element for gas molecule sensing apparatus for gas molecule and method for sensing gas molecule |
| MX2013006138A (en) * | 2013-05-31 | 2014-12-01 | Univ Nac Autónoma De México | Porphyrinûpyrene compounds with a high energy transference. |
| CN106349248A (en) * | 2016-08-09 | 2017-01-25 | 济南大学 | Metalloporphyrin complex and preparation method and application thereof |
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| CN102687001A (en) * | 2010-08-05 | 2012-09-19 | 松下电器产业株式会社 | Sensing element for gas molecule sensing apparatus for gas molecule and method for sensing gas molecule |
| MX2013006138A (en) * | 2013-05-31 | 2014-12-01 | Univ Nac Autónoma De México | Porphyrinûpyrene compounds with a high energy transference. |
| CN106349248A (en) * | 2016-08-09 | 2017-01-25 | 济南大学 | Metalloporphyrin complex and preparation method and application thereof |
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| Title |
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| Glucose fuel cell based on carbon nanotube-supported pyrene-metalloporphyrin catalysts;Elouarzaki, K. 等;《JOURNAL OF MATERIALS CHEMISTRY A》;20161231;全文 * |
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