CN106349247A - 5-p-hydroxyphenyl-10,15,20-trichlorophenyl porphyrin nanotube and preparation method and application thereof - Google Patents

5-p-hydroxyphenyl-10,15,20-trichlorophenyl porphyrin nanotube and preparation method and application thereof Download PDF

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CN106349247A
CN106349247A CN201610647411.9A CN201610647411A CN106349247A CN 106349247 A CN106349247 A CN 106349247A CN 201610647411 A CN201610647411 A CN 201610647411A CN 106349247 A CN106349247 A CN 106349247A
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htclpp
trichlorophenyl
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hydroxybenzene
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CN106349247B (en
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王榆成
朱沛华
宋非非
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University of Jinan
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    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
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Abstract

The invention relates to a 5-p-hydroxyphenyl-10,15,20-trichlorophenyl porphyrin nanotube and a preparation method and application thereof and belongs to the technical field of organic semiconductor material chemistry. The 5-p-hydroxyphenyl-10,15,20-trichlorophenyl porphyrin (p-HTClPP) nanotube is prepared successfully for the first time. The preparation method includes the preparation steps of (1), dissolving p-HTClPP with a specific solvent so as to obtain a 0.006-0.012 mmol/mL solution; (2), soaking a treated AAO template in the solution prepared in the step (1), standing for 7-10 hours hermetically and removing residual solution prior to vacuum drying; (3) using a 3 mol/L sodium hydroxide water solution for dissolving away AAO in a p-HTClPP nanotube containing the AAO template prepared in the step (2). The preparation method has the advantages of simplicity, easiness in experiment process control and capability of being operated at a room temperature. The 5-p-hydroxyphenyl-10,15,20-trichlorophenyl porphyrin nanotube is capable of effectively detecting nitrogen dioxide gas at the room temperature and is low in NO2 response concentration, high in sensitivity and capable of resisting interference of reduced gas (CO and NH3).

Description

A kind of 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano pipe and its preparation Methods and applications
Technical field
The present invention relates to a kind of 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano pipe and preparation method thereof and Application, belongs to organic semiconducting materials technical field of chemistry.
Background technology
With modern furniture, coal, automobile and other industries development, the burning of various fuel and the construction in chemical plant, to In air, the toxic gas of discharge gets more and more.In such as indoor decorating and refurnishing materials, plywood, core-board, Midst density are fine The formaldehyde of release in the particieboard of dimension plate, wall covering fabric, patch wall chemical fibre carpet, foam plasticss, paint and coating；Paint, various oil The benzene of release in the additive of paint coating and diluent, adhesive, waterproof material；Fuel combustion, transportation, smoking, the cooking In smog, furniture, tvoc in household electrical appliance etc.；These gas toxics are very big.Therefore, how quick and accurate Detection and the control toxic gas of low concentration become problem demanding prompt solution.In these gases, nitrogen dioxide (no2) as nitrogen One kind of oxide, is a kind of toxic gas of rufous with penetrating odor, strong oxidizing property, is also atmospheric pollution simultaneously One of thing.It derives from the exhaust emissions of automobile motor vehicles, the life of the burning of fuel, commercial production and lightning and microorganism Life activity etc., both can form photochemical fog it is also possible to form acid rain it is often more important that the murder by poisoning to human body is quite big, because How this detects and to control to it is just particularly important.Gas sensor can be with fast monitored toxic gas no2Presence, from And can timely and effectively be controlled.
Now people concentrate on two classes to the research of gas sensor: Metal Oxide Semiconductor Gas Sensing sensor and organic Semiconductor gas sensor.Wherein the former studies more than the latter, is preferably applied in production practices, but blemish in an otherwise perfect thing It is that the former preparation technology is relatively complicated, production cost is higher, and operating temperature range is higher, needs to consume the substantial amounts of energy. On the contrary, the latter's (organic semiconductor gas sensor) can use at room temperature, significantly reduces the use of gas sensor Condition, for this positive research and development organic semiconducting materials made gas sensor element and cause researchers greatly emerging Interest.At present, porphyrin, phthalocyanines macromole have unique π-pi-conjugated structure, are conducive to the quick flowing of electronics, therefore easily Show the property of quasiconductor；When gas molecule is contacted with these organic semiconducting materials, interelectric transfer can occur, lead Send a telegraph stream can change.In addition, numerous studies show that nanotube has higher specific surface area, this is beneficial to gas molecule Substantial amounts of diffusion in pipe, greatly increases collision probability therebetween, thus reaching to toxic gas Old plant Purpose.Therefore synthesize such organic semiconducting materials and be prepared into nano tubular structure there is certain practical significance.
Content of the invention
The present invention first consists in a kind of 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano pipe of offer and its system Preparation Method and application.
Technical scheme
A kind of 5- p-hydroxybenzene -10, the preparation method of 15,20- trichlorophenyl porphyrin nano pipes, its preparation process is such as Under:
(1) by 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrins are dissolved with specific solvent, prepare 0.006- The solution of 0.012mmol/ml；
Described 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrins, referred to as (p-htclpp), its structural formula such as formula 1 institute Show；
Described solvent is oxolane (thf) or mixed solvent；Mixed solvent is by dichloromethane: methanol=5:1 (volume Than) composition；
(2) by aperture, the anodic oxidation aluminium formwork (aao) for 110nm is immersed in solvent prepared by step (1), and sealing is quiet Put 7-10h, then surplus solution is removed, vacuum drying, obtain the p-htclpp nanotube of template containing aao；
(3) in the p-htclpp nanotube containing aao template with the sodium hydrate aqueous solution of 3mol/l prepared by step (2) Aao dissolve；
Formula 1:
The selection of above-mentioned preparation process, wherein step (1) solvent and solution concentration prepare p-htclpp nanotube Core.First, it is not that p-htclpp nanotube can be prepared using any good solvent；Such as, if being respectively adopted two , as good solvent, other conditions keep constant, then can not prepare p-htclpp nanotube for chloromethanes or absolute methanol；And press According to dichloromethane: the method for methanol=5:1 (volume ratio) two kinds of solvents are mixed after as solvent, it is found that p- can be prepared Htclpp nanotube；This illustrates that a certain proportion of mixed solvent can prepare nanotubes effectively.Secondly, if prepared solution Concentration is more than 0.012mmol/ml, nor prepares p-htclpp nanotube, but prepares irregular aggregate structure；If institute The solution concentration of preparation is less than 0.006mmol/ml, same nor prepare p-htclpp nanotube, but is prepared into and does not advise Nanometer chip architecture then；From this it can be concluded that suitable solution concentration (0.006-0.012mmol/ml) is to prepare p- The key of htclpp nanotube.
Above-mentioned preparation process, during step (2) " and then removing surplus solution ", in order to obtain ordered structure, all Even scattered p-htclpp nanotube, keeps aao template motionless；So can reduce p-htclpp nanotube disorderly arranged with And damaged degree.It is preferred, therefore, that taking the method for " being removed solution with dropper " to remove solution.
Above-mentioned preparation process is it is preferred that step (3) " aao in (p-htclpp) nanotube containing aao template dissolves " Afterwards, carry out being centrifuged repeatedly cleaning with distilled water, till wash clean.
Secondly the present invention additionally provides a kind of 5- p-hydroxybenzene -10,15,20- trichloro-benzenes of utilization said method preparation Base porphyrin nano pipe.
Above-mentioned 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano pipes, its length is 100 μm, and aperture is 110nm, wall thickness is 10-20nm.
5- p-hydroxybenzene -10 of above-mentioned preparation, 15,20- trichlorophenyl porphyrin nano pipes, tube wall is by 5- para hydroxybenzene The nano ordered aggregation of base -10,15,20- trichlorophenyl porphyrin is constituted.In these nanotubes, rely on intermolecular phase Interaction, that is, π-the π between porphyrin ring interacts and Hyarogen-bonding forms orderly aggregate structure.The tube wall of nanotube by The planar structure of orderly porphyrin ring is constituted, and its normal direction is axially vertical with pipe.
5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano the pipe of above-mentioned preparation, to toxic gas no2Have Preferably air-sensitive response: 1. p-htclpp nanotube and no2During molecule contacts, no2As electron acceptors, p-htclpp conduct , there is therebetween interelectric transfer in electron donor, and nano tubular structure can improve interelectric rate travel, makes The electronics of p-htclpp drastically declines, thus leading to electric current to decline.2. p-htclpp nanotube has that specific surface area is big, Kong Duoer Intensive advantage, this makes itself and no2The contact probability of molecule greatly increases, and is conducive to no simultaneously2On gas sensitive surface and interior Portion adsorbs and desorbing faster, thus improving response and the recovery time of air-sensitive.3. p-htclpp nanotube is to no2Have good Selectivity, reducibility gas can be resisted (as co and nh simultaneously3) interference.
And then the present invention provides the 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano pipe of above-mentioned preparation Practical application, that is, be used for toxic gas no2Detection.The organic semiconducting materials nanotube of above-mentioned preparation is at room temperature to no2 There is good detection range (5-100ppm)；At room temperature to no2The lowest detection limit be 5ppm, and response time and Recovery time is respectively 240s and 1080s.
Present invention also offers a kind of preparation method of gas sensor, its preparation process is as follows:
(1) 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano pipe is dispersed in distilled water；
(2) the 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin nano Guan Jun of 0.5-1mg is carefully drawn with dropper Even drop coating, in the interdigital electrode of ito electro-conductive glass, is vacuum dried, you can obtain the gas sensor for testing air-sensitive performance.
Beneficial effect
(1) present invention has successfully prepared 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin p-htclpp first and has received Mitron；
(2) the gas sensor preparation process is simple of present invention preparation, cost is relatively low, just can operate at room temperature.
(3) the 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin p-htclpp nanotube pattern of present invention preparation can Control, is just able to detect that no at ambient temperature2Presence, and test limit is relatively low, sensitivity is high, simultaneously to no2Have good Selectivity, reducibility gas (co and nh can be stoped3) interference, have broad application prospects in air-sensitive field.
Brief description
Sem figure (a: after soaking 7h of the p-htclpp nanotube of Fig. 1 embodiment 1；B: after supersound process；C: single p- The mouth of pipe of htclpp nanotube)；
The electronic of the p-htclpp nanotube that Fig. 2 p-htclpp solution and embodiment 1 obtain；Solid line is p- Htclpp solution, dotted line is p-htclpp nanotube；
The xrd collection of illustrative plates of the p-htclpp nanotube that Fig. 3 embodiment 1 obtains and cell configuration schematic diagram；
Fig. 4 p-htclpp powder and the infared spectrum of p-htclpp nanotube；(wherein a is p-htclpp powder, and b is p- Htclpp nanotube)；
The eds collection of illustrative plates of the p-htclpp nanotube that Fig. 5 embodiment 1 obtains；
The structural representation of Fig. 6 gas sensor；
The cross-sectional view of Fig. 7 gas sensor；
The current -voltage curve of the gas sensor that Fig. 8 embodiment 2 obtains；
The gas sensor that Fig. 9 embodiment 2 obtains is to no2Current versus time curve；
The gas sensor that Figure 10 embodiment 2 obtains is to 100ppm no2Dynamic response curve；
The gas sensor that Figure 11 embodiment 2 obtains is to no2Sensitivity-concentration curve；
The current versus time curve to co for the gas sensor that Figure 12 embodiment 2 obtains；
The gas sensor that Figure 13 embodiment 2 obtains is to nh3Current versus time curve；
Fig. 6, in 7,1 is ito clear glass substrate, and 2 is interdigital electrode, and 3 is the coating of p-htclpp nanotube.
Specific embodiment
Embodiment 1
1.1
1. aperture is the anodic oxidation aluminium formwork (aao) of 110nm respectively with distilled water → dehydrated alcohol → acetone → trichlorine Methane is cleaned by ultrasonic 10min；
2. weigh 0.007mmol p-htclpp to be dissolved in 1ml thf (oxolane), the aao processing template is soaked Bubble, in the p-htclpp solution preparing, suctions out remaining solution after standing 8h, vacuum drying；Template containing aao can be obtained P-htclpp nanotube.
3. dissolve aao template with the sodium hydrate aqueous solution of 3mol/l, solution is centrifuged in centrifuge, remove upper strata Clear liquid, retains lower floor's product.
4. lower floor's solid distilled water is cleaned repeatedly, can get p-htclpp nanotube after wash clean, use distilled water By its dispersed after carry out next step test.
Prepared nanotube is characterized: observe its pattern using scanning electron microscope (sem) and understand to be nanometer Tubular structure, is h accumulation type arrangement mode by the molecule that ultra-violet absorption spectrum and x-ray diffraction understand nanotube walls.In addition, Prove that nanotube is made up of p-htclpp by infrared spectrum and x-ray power spectrum (eds).
1.2
1. aperture is the anodic oxidation aluminium formwork (aao) of 110nm respectively with distilled water → dehydrated alcohol → acetone → trichlorine Methane is cleaned by ultrasonic 10min；
2. weigh 0.012mmol p-htclpp to be dissolved in 1ml thf (oxolane), the aao processing template is soaked Bubble, in the p-htclpp solution preparing, suctions out remaining solution after standing 8h, vacuum drying；Template containing aao can be obtained P-htclpp nanotube.
3. dissolve aao template with the sodium hydrate aqueous solution of 3mol/l, solution is centrifuged in centrifuge, remove upper strata Clear liquid, retains lower floor's product.
4. lower floor's solid distilled water is cleaned repeatedly, can get p-htclpp nanotube after wash clean, use distilled water By its dispersed after carry out next step test.
The solid product obtaining is characterized comprehensively: result is consistent with 1.1.
1.3
1. aperture is the anodic oxidation aluminium formwork (aao) of 110nm respectively with distilled water → dehydrated alcohol → acetone → trichlorine Methane is cleaned by ultrasonic 10min；
2. weigh 0.012mmol p-htclpp to be dissolved in 1ml mixed solvent (described mixed solvent is by dichloromethane and first Alcohol forms according to the volume ratio of 5:1) in, the aao processing template is immersed in the p-htclpp solution preparing, stands 8h After suction out remaining solution, vacuum drying；The p-htclpp nanotube containing aao template can be obtained.
3. dissolve aao template with the sodium hydrate aqueous solution of 3mol/l, solution is centrifuged in centrifuge, remove upper strata Clear liquid, retains lower floor's product.
4. lower floor's solid distilled water is cleaned repeatedly, can get p-htclpp nanotube after wash clean, use distilled water By its dispersed after carry out next step test.
The solid product obtaining is characterized comprehensively: result is consistent with 1.1.
1.4
1. aperture is the anodic oxidation aluminium formwork (aao) of 110nm respectively with distilled water → dehydrated alcohol → acetone → trichlorine Methane is cleaned by ultrasonic 10min；
2. weigh 0.006mmol p-htclpp to be dissolved in 1ml mixed solvent (described mixed solvent is by dichloromethane and first Alcohol forms according to the volume ratio of 5:1) in, the aao processing template is immersed in the p-htclpp solution preparing, standing Remaining solution is suctioned out, vacuum drying after 10h；The p-htclpp nanotube containing aao template can be obtained.
3. dissolve aao template with the sodium hydrate aqueous solution of 3mol/l, solution is centrifuged in centrifuge, remove upper strata Clear liquid, retains lower floor's product.
4. lower floor's solid distilled water is cleaned repeatedly, can get p-htclpp nanotube after wash clean, use distilled water By its dispersed after carry out next step test.
The solid product obtaining is characterized comprehensively: result is consistent with 1.1.
Embodiment 2
1. ito electro-conductive glass substrate is cleaned by ultrasonic three times respectively with toluene → acetone → ethanol → deionized water successively, 5min, then dry for standby.
2. the careful drop coating of p-htclpp nanotube preparing 1mg embodiment 1 is to dried ito electro-conductive glass base In the interdigital electrode of piece, vacuum drying, that is, obtain the gas sensor of gas sensor.
Embodiment 3
It is assembled into the air-sensitive test device of p-htclpp nanotube with the gas sensor that embodiment 2 prepares, for no2 Air-sensitive measure.Wherein whole test process fixed-bias transistor circuit between two electrodes is to carry out under 5v and room temperature condition.Make Use test instrunment model: Agilent b290a precision source/measuring unit.Wherein, received using the p-htclpp that embodiment 1 prepares The gas sensor that mitron is prepared further is repeatedly tested, and result is consistent；As shown in figures 8-13.As shown in figure 8, the present invention The p-htclpp nanotube gas sensor of preparation has higher conductive capability.Fig. 9 shows p-htclpp nanotube gas sensing The no to 5-100ppm for the device2There is good air-sensitive response, and response time and recovery time are respectively 240s and 1080s. Figure 10 illustrates the no to 100ppm for the p-htclpp nanometer tube gas sensitive sensor2Stability preferable.Figure 11 shows that p-htclpp receives Air-sensitive response (sensitivity) of mitron gas sensor and no2Concentration assumes linear relationship in low strength range.Figure 12,13 proofs P-htclpp nanometer tube gas sensitive sensor is to co and nh3Do not respond to, to no2There is good selectivity.In sum, p- Htclpp nanometer tube gas sensitive sensor is to no2There is the advantages such as response concentration is low, good stability, sensitivity height, selectivity are strong, Air-sensitive has actual application value in field.

Claims (10)

1. a kind of 5- p-hydroxybenzene -10, the preparation method of 15,20- trichlorophenyl porphyrin nano pipes is it is characterised in that include Following steps:
(1) by 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrins specific solvent dissolves, and is prepared into 0.006- The solution of 0.012mmol/ml；
Described 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrins, abbreviation p-htclpp, its structural formula is as shown in Equation 1；
Described specific solvent is oxolane (thf) or mixed solvent；Described mixed solvent is by dichloromethane: absolute methanol= 5:1 (volume ratio) forms；
(2) by aperture, the aao template for 110nm is immersed in solution prepared by step (1), static placement 7-10h；Then will remain Remaining solution removes, vacuum drying, obtains the p-htclpp nanotube containing aao template；
(3) with the sodium hydrate aqueous solution of 3mol/l, the aao in the p-htclpp nanotube containing aao template is dissolved.
Formula 1:
2. preparation method according to claim 1, it is characterised in that step (2), adopts and " is removed surplus solution with dropper Go " mode " surplus solution is removed ".
3. preparation method according to claim 1 and 2 it is characterised in that step (3) " p-htclpp containing aao template receives Aao in mitron dissolves " after, carry out being centrifuged repeatedly cleaning with distilled water.
4. the 5- p-hydroxybenzene -10,15,20- trichlorine of preparation method preparation described in a kind of employing claim 1-3 any one Phenyl porphyrin nano pipe.
5. 5- p-hydroxybenzene -10 according to claim 4,15,20- trichlorophenyl porphyrin nano pipes it is characterised in that Its length is 100 μm, and aperture is 110nm, and wall thickness is 10-20nm.
6. 5- p-hydroxybenzene -10 according to claim 4 or 5,15,20- trichlorophenyl porphyrin nano pipes, its feature exists In its tube wall is to be made up of the planar structure of orderly porphyrin ring, and the normal direction of its planar structure is hung down with the axial direction of nanotube Directly.
7. 5- p-hydroxybenzene -10 described in a kind of claim 4,5 or 6,15,20- trichlorophenyl porphyrin nano pipes, its feature It is, for detecting toxic gas no2Presence.
8. purposes according to claim 7 is it is characterised in that at room temperature to no2The lowest detection limit be 5ppm.
9. purposes according to claim 8 is it is characterised in that no to 5-100ppm2Response time and divide recovery time Wei not 240s and 1080s.
10. a kind of gas being prepared into using 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin described in claim 4,5 or 6 Quick element.
CN201610647411.9A 2016-08-09 2016-08-09 A kind of 5- p-hydroxybenzenes -10,15,20- trichlorophenyl porphyrin nano pipes and its preparation method and application Expired - Fee Related CN106349247B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915841A (en) * 2017-11-15 2018-04-17 复旦大学 Can the conversion of efficient catalytic carbon dioxide poly- phthalocyanin nano material and its preparation method and application
CN109254037A (en) * 2018-08-30 2019-01-22 浙江理工大学 A kind of preparation method of the metalloporphyrin nanotube of modified by graphene quantum dot-cadmium sulfide complex light sensitive sensing material
CN113773260A (en) * 2021-08-26 2021-12-10 华南师范大学 Covalent-like organic material and preparation method and application thereof

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CN101671340A (en) * 2009-09-30 2010-03-17 中山大学 Carboxyl porphyrin and preparation method thereof
CN104865292A (en) * 2015-04-27 2015-08-26 济南大学 Nitrogen dioxide gas sensor based on o-aminophenyl substituted porphyrin nanometer material
CN105223237A (en) * 2015-09-10 2016-01-06 济南大学 A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO 2gas sensor

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CN101671340A (en) * 2009-09-30 2010-03-17 中山大学 Carboxyl porphyrin and preparation method thereof
CN104865292A (en) * 2015-04-27 2015-08-26 济南大学 Nitrogen dioxide gas sensor based on o-aminophenyl substituted porphyrin nanometer material
CN105223237A (en) * 2015-09-10 2016-01-06 济南大学 A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO 2gas sensor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915841A (en) * 2017-11-15 2018-04-17 复旦大学 Can the conversion of efficient catalytic carbon dioxide poly- phthalocyanin nano material and its preparation method and application
CN107915841B (en) * 2017-11-15 2020-05-12 复旦大学 Poly phthalocyanine nano material capable of efficiently catalyzing carbon dioxide conversion and preparation method and application thereof
CN109254037A (en) * 2018-08-30 2019-01-22 浙江理工大学 A kind of preparation method of the metalloporphyrin nanotube of modified by graphene quantum dot-cadmium sulfide complex light sensitive sensing material
CN109254037B (en) * 2018-08-30 2020-07-14 浙江理工大学 Preparation method of graphene quantum dot modified metalloporphyrin nanotube-cadmium sulfide composite photosensitive sensing material
CN113773260A (en) * 2021-08-26 2021-12-10 华南师范大学 Covalent-like organic material and preparation method and application thereof
CN113773260B (en) * 2021-08-26 2023-09-22 华南师范大学 Covalent-like organic material and preparation method and application thereof

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