CN106349248A - Metalloporphyrin complex and preparation method and application thereof - Google Patents
Metalloporphyrin complex and preparation method and application thereof Download PDFInfo
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- CN106349248A CN106349248A CN201610648227.6A CN201610648227A CN106349248A CN 106349248 A CN106349248 A CN 106349248A CN 201610648227 A CN201610648227 A CN 201610648227A CN 106349248 A CN106349248 A CN 106349248A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- 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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- G—PHYSICS
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Abstract
The invention relates to a metalloporphyrin complex and a preparation method and application thereof, and belongs to the technical field of organic semiconductor materials. The metalloporphyrin complex p-HTClPPCo is synthesized successively for the first time, and a p-HTClPPCo nanotube is prepared for the first time. A preparation process of the metalloporphyrin complex is as follows: (1) dissolving p-HTClPPCo with a specific solvent, and preparing into 0.005-0.010 mmol/mL of solution; (2) soaking a treated AAO template in the solution prepared in the step (1), standing for 7-10 hours in a sealed manner, then removing residua solution, and drying under vacuum; and (3) dissolving AAO in the AAO-template-containing p-HTClPPCo nanotube prepared in the step (2) with 3 mol/L of a sodium hydroxide aqueous solution to obtain the final product. The metalloporphyrin complex and the preparation method and application thereof have the advantages that a preparation process is quite simple, an experiment process is easy to control, and experiments can operate at room temperature. In addition, a prepared p-HTClPPCo nanotube gas sensor can effectively detect NO2 gas at room temperature; concentration of response to NO2 is relatively, response is quick, and sensitivity is high; and interference of reducing gas (CO and NH3) can be resisted, and the metalloporphyrin complex can be widely used for detecting NO2.
Description
Technical field
The present invention relates to a kind of Metalloporphyrins and its preparation method and application, belong to organic semiconducting materials chemistry
Technical field.
Background technology
With industrialized continuous development, the industry such as electric welding, plating, smelting, chemical industry, oil in actual production process not
Toxic compounds can be produced with avoiding.The formaldehyde of release in such as building and ornament materials and article of furniture；Paint, glue, coating and
The benzene of release and benzene homologues in putty；The ammonia of release in concrete admixture；The radon of release in granite, marble, Gypsum Fibrosum
Tvoc of release etc. in gas and domestic gas, fire coal, tobacco smoke, industrial waste gas, vehicle exhaust, photochemical pollution.These
The hazardness of compound is very big, and some even influence whether the life and health of people.Therefore, quick detection control these poisonous
Material has become as the problem now having to solve.Nitrogen dioxide (no2) as nitrogen oxides one kind, be a kind of brownish red
And the toxic gas of irritant stink.It is mainly derived from the discharge of vehicle exhaust, the burning of fuel and nitric acid, nitrogenous fertilizer processing
Factory, nitration processes, nitrate industrial processes medium.Both photochemical fog can have been formed it is also possible to form acid rain, thus
The normal operation of harm ecosystem sucks excessive no it is often more important that working as human body2When lung airways are had strong
Stimulation, can cause lung damage even to cause pulmonary edema, and chronic poisoning leads to trachea, pneumonopathy to become etc., the harm phase to human body
When big.Therefore it is carried out with effective detection and control just seems particularly important.And gas sensor can sensitively detect no2Gas
Body, by the extensive concern of researchers.
So far, people mainly include metal-oxide semiconductor (MOS) and organic compound half to the research of gas sensor
Conductor two big class.Wherein metal-oxide (zno, cuo, wo3Deng) semi-conducting material due to relatively low excite with reference to can and relatively
Wide band gap is widely used in produce reality, but regrettably processing technology is relatively complicated, produce into
This height, and operating temperature height (400-500 DEG C), power consumption is big.In contrast, organic compound (porphyrin and metalloporphyrin
Class, phthalocyanine and metal phthalocyanine class) semi-conducting material just can work in room temperature it is easy to process and the low advantage of production cost, with
When there are response recovery characteristics faster to toxic gas, in recent years gradually substituted metal oxide semiconductor material and obtain big
The application of amount.Improve the interaction that the key of air-sensitive performance is to increase between gas molecule and material surface, the nanometer of porous
Tubular construction increases the binding site between pipe inside and Guan Yuguan, is conducive to the transfer of electric charge and the absorption of gas molecule to conciliate
Inhale.Therefore, prepare the gas sensor of organic semiconductor nano material and be applied to air-sensitive Journal of Sex Research there is certain reality
With being worth.
Content of the invention
The practical problem that the present invention solves is to provide a kind of Metalloporphyrins and its preparation method and application.
Technical scheme
A kind of Metalloporphyrins, referred to asp- htclppco, its structural formula, as shown in Equation 1:
Formula 1
The preparation method of above-mentioned Metalloporphyrins, comprises the steps:
(1) under 90-110 DEG C of temperature conditionss, 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrins and cobaltous acetate, with
N, n- dimethylformamide (dmf) be medium, with nitrogen as protective gas, stirring reaction 8-10 hour；5- p-hydroxybenzene-
The mol ratio of 10,15,20- trichlorophenyl porphyrin and cobaltous acetate is 1:7-10；
(2) it is cooled to room temperature after the completion of reacting, adds distilled water, with n, the volume ratio of n- dimethylformamide is 1:2-3, standing
1-2h, filters, and uses distilled water and washing with alcohol respectively, obtains target product；
(3), in order to improve the purity of product, in step (2), products therefrom plus chloroform dissolving are tied with methanol again
Brilliant；The mol ratio of chloroform and methanol is 1:5-8.Wherein, as good solvent, methanol is as poor solvent for chloroform.
Above-mentioned MetalloporphyrinspThe nanotube of-htclppco, its preparation process is as follows:
(1) by above-mentioned Metalloporphyrinsp- htclppco specific solvent dissolves, and obtains 0.005 mmol ~ 0.010
The solution of mmol/ml；Described solvent is oxolane (thf) or mixed solvent；Mixed solvent is by dichloromethane: methanol=
5:1 (volume ratio) forms；
(2) anodic oxidation aluminium formwork (aao) that aperture is 110 nm is immersed in solvent prepared by step (1), sealing
Then surplus solution is removed by standing 7-10 h, and vacuum drying obtains template containing aaop- htclppco nanotube；
(3) with the sodium hydrate aqueous solution of 3 mol/l by step (2) prepare containing aao templatep- htclppco nanotube
In aao dissolve；
Above-mentioned MetalloporphyrinspThe selection of-htclppco nanotube, wherein step (1) solvent and solution concentration are
PreparationpThe core of-htclppco nanotube.
First, it is not can be prepared using any good solventp-htclppco；Such as, if being respectively adopted three
, as good solvent, other conditions keep constant, then can not prepare for chloromethanes or absolute methanolp- htclppco nanotube；
And according to dichloromethane: the method for absolute methanol=5:1 (volume ratio) two kinds of solvents are mixed after as solvent, it is found that
Can preparep- htclppco nanotube；This illustrates that a certain proportion of mixed solvent can prepare nanotubes effectively.
Secondly, if prepared solution concentration is more than 0.010mmol/ml, nor preparep- htclppco nanometer
Pipe, but it is prepared into irregular flaky nanometer structure；If prepared solution concentration is less than 0.005 mmol/ml, equally
Can not preparep- htclppco nanotube, but it is prepared into irregular mealy structure；From this it can be concluded that it is suitable
Solution concentration (0.005-0.010 mmol/ml) be to preparepThe key of-htclppco nanotube.
Above-mentioned Metalloporphyrinsp- htclppco nanotube, the mistake of step (2) " and then surplus solution is removed "
Cheng Zhong, in order to obtain ordered structure, homodispersep- htclppco nanotube, keeps aao template motionless；So can subtract
FewpThe disorderly arranged and damaged degree of-htclppco nanotube.It is preferred, therefore, that taking " being removed solution with dropper "
Method solution is removed.
Above-mentioned Metalloporphyrinsp- htclppco nanotube is it is preferred that step (3) is " containing aao templatep-
Aao in htclppco nanotube dissolves " after, carry out being centrifuged repeatedly cleaning with distilled water, till wash clean.
Above-mentioned Metalloporphyrinsp- htclppco nanotube, its length is 100 μm, and aperture is 110 nm, wall thickness
For 10-20 nm.
Above-mentioned have Metalloporphyrinsp- htclppco nanotube, tube wall be by plane distribution 5- p-hydroxybenzene-
The nano ordered aggregation of 10,15,20- trichlorophenyl Cobalt Porphyrin is constituted.In these nanotubes, rely on intermolecular phase
Interaction, that is, π-the π between porphyrin ring interacts and the effect of metal-complexing key forms orderly aggregate structure.The pipe of nanotube
Wall is made up of the planar structure of orderly metalloporphyrin ring, and its normal direction is axially in parallel with pipe.
Above-mentioned Metalloporphyrinsp- htclppco nanotube, to toxic gas no2There is preferable air-sensitive respond:
①p- htclppco nanotube and no2During molecule contacts, no2As electron acceptors,p- htclppco gives as electronics
, there is therebetween interelectric transfer in the person of giving, and nano tubular structure can improve interelectric rate travel, makesp-
The electronics of htclppco drastically declines, thus leading to electric current to decline.②p- htclppco nanotube has that specific surface area is big, hole
Many and intensive advantages, this makes itself and no2The contact probability of molecule greatly increases, and is conducive to no simultaneously2On gas sensitive surface
Adsorb faster and desorbing with inside, thus improving response and the recovery time of air-sensitive.③p- htclppco nanotube is to no2
There is good selectivity, reducibility gas can be resisted (as what nh of co simultaneously3) interference.
And then the present invention provides above-mentioned Metalloporphyrinsp- htclppco nanotube is answered real-life
With being used for toxic gas no2Detection.The Metalloporphyrins of above-mentioned preparationp- htclppco nanotube is at room temperature
To no2There is wider detection range (500 ppb -100 ppm)；At room temperature to no2The lowest detection limit be 500
Ppb, and response time and recovery time are respectively 240 s and 695 s.
Present invention also offers a kind of system of the gas sensor being prepared from using above-mentioned Metalloporphyrins nanotube
Preparation Method, its preparation process is as follows:
(1) 5- p-hydroxybenzene -10,15,20- trichlorophenyl Cobalt Porphyrin nanotube is dispersed in distilled water；
(2) with dropper carefully draw 0.5-1 mg 5- p-hydroxybenzene -10,15,20- trichlorophenyl Cobalt Porphyrin nanotube equal
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 a kind of Metalloporphyrins firstp-htclppco.
(2) present invention has successfully prepared a kind of Metalloporphyrins nanotube firstp- htclppco nanotube.
(3) present invention preparation Metalloporphyrins nanometer tube gas sensitive sensor preparation process is simple, cost relatively low,
Just can operate under room temperature.
(4) the Metalloporphyrins nanotube morphology controllable of present invention preparation, is just able to detect that at ambient temperature
no2Presence, and test limit is relatively low, sensitivity is high, simultaneously to no2There is good selectivity, reproducibility gas can not be subject to
Body (co and nh3) interference.Have broad application prospects in air-sensitive field.
Brief description
Fig. 1 MetalloporphyrinspThe mass spectrum of-htclppco；
Fig. 2 MetalloporphyrinspThe proton nmr spectra of-htclppco；
Fig. 3 embodiment 2pSem figure (a: after soaking 7h of-htclppco nanotube；B: after supersound process；C: singlep
The mouth of pipe of-htclppco nanotube)；
Fig. 4p- htclppco solution and embodiment 2 obtainpThe ultra-violet absorption spectrum of-htclppco nanotube；Solid line
Forp- htclppco solution, dotted line isp- htclppco nanotube.
Fig. 5 embodiment 2 obtainspThe xrd collection of illustrative plates of-htclppco nanotube and cell configuration schematic diagram；
Fig. 6p- htclppco powder andpThe infared spectrum of-htclppco nanotube；(wherein a isp- htclppco powder,
B isp- htclppco nanotube)
Fig. 7 embodiment 2 obtainspThe eds collection of illustrative plates of-htclppco nanotube；
The structural representation of Fig. 8 gas sensor；
The cross-sectional view of Fig. 9 gas sensor；
The current -voltage curve of the gas sensor that Figure 10 embodiment 3 obtains；
The gas sensor that Figure 11 embodiment 3 obtains is to no2Current versus time curve；
The gas sensor that Figure 12 embodiment 3 obtains is to 100 ppm no2Dynamic response curve；
The gas sensor that Figure 13 embodiment 3 obtains is to no2Sensitivity-concentration curve；
The current versus time curve to co for the gas sensor that Figure 14 embodiment 3 obtains；
The gas sensor that Figure 15 embodiment 3 obtains is to nh3Current versus time curve；
Fig. 8, in 9,1 is ito clear glass substrate, and 2 is interdigital electrode, and 3 arepThe coating of-htclppco nanotube.
Embodiment 1
1.1
By 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin (50 mg, 0.06 mmol) and cobaltous acetate (50 mg,
0.42 mmol) it is dissolved in dimethylformamide (15ml), with nitrogen as protective gas, react 8 hours under the conditions of 100 DEG C.Reaction
After the completion of be cooled to room temperature, plus distilled water 30 ml, stand 1-2 h, filter, use distilled water and washing with alcohol respectively, obtain target
Product.Product 5ml chloroform is dissolved, is carefully added into 30ml methanol, stands overnight, obtain dark red powder 32mg, yield
64 %.Mass spectrum as shown in figure 1, mass spectrographic molecular ion peak be 792.122, theoretical value 790.987, dark red powder is described
Forp-htclppco.Hydrogen nuclear magnetic resonance spectrogram (cdcl3, 600 mhz) as shown in Fig. 2 wherein δ (ppm): 8.92 (d,
2h), 8.86 (d, 6h), 8.2(d, 6h), 8.1 (d, 2h), 7.3 (d, 6h), 7.2 (d, 2h), 5.3
(br, 1h).Illustrate that this dark red powder is target productp-htclppco.
1.2
By 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin (50 mg, 0.06 mmol) and cobaltous acetate (71 mg,
0.60 mmol) it is dissolved in dimethylformamide (10 ml), with nitrogen as protective gas, react 8 hours under the conditions of 110 DEG C.Instead
It is cooled to room temperature after the completion of answering, plus distilled water 30 ml, stand 1-2h, filter, use distilled water and washing with alcohol respectively, obtain mesh
Mark product.Product 5ml chloroform is dissolved, is carefully added into 35 ml methanol, stands overnight, obtain dark red powder 36mg, produce
Rate 72%.Mass spectrum as shown in figure 1, mass spectrographic molecular ion peak be 792.122, theoretical value 790.987, dark red toner is described
End isp-htclppco.Hydrogen nuclear magnetic resonance spectrogram (cdcl3, 600 mhz) as shown in Fig. 2 wherein δ (ppm): 8.92
(d, 2h), 8.86 (d, 6h), 8.2(d, 6h), 8.1 (d, 2h), 7.3 (d, 6h), 7.2 (d, 2h), 5.3
(br, 1h).Illustrate that this dark red powder is target productp-htclppco.
1.3
By 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrin (50 mg, 0.06 mmol) and cobaltous acetate (50 mg,
0.42 mmol) it is dissolved in dimethylformamide (15 ml), with nitrogen as protective gas, react 10 hours under the conditions of 110 DEG C.Instead
It is cooled to room temperature after the completion of answering, plus distilled water 30 ml, stand 1-2 h, filter, use distilled water and washing with alcohol respectively, obtain mesh
Mark product.Product is dissolved with 5 ml chloroform, is carefully added into 30ml methanol, stands overnight, obtain dark red powder 40 mg,
Yield 80%.Mass spectrum as shown in figure 1, mass spectrographic molecular ion peak be 792.122, theoretical value 790.987, kermesinus is described
Powder isp-htclppco.Hydrogen nuclear magnetic resonance spectrogram (cdcl3, 600 mhz) as shown in Fig. 2 wherein δ (ppm): 8.92
(d, 2h), 8.86 (d, 6h), 8.2(d, 6h), 8.1 (d, 2h), 7.3 (d, 6h), 7.2 (d, 2h), 5.3
(br, 1h).Illustrate that this dark red powder is target productp-htclppco.
Embodiment 2
2.1
Anodised aluminium (aao) template that aperture is 110 nm uses distilled water, dehydrated alcohol, acetone and chloroform etc. successively
The solvent supersonic cleaning 10min of opposed polarity, dry for standby.
1. weigh 0.005 mmolp- htclppco is dissolved in 1 ml thf (oxolane), by the aao processing
Template is immersed in the solution preparing, and suctions out remaining solution after sealing and standing 8h, vacuum drying；Mould containing aao can be obtained
Platep- htclppco nanotube.
2. dissolve aao template with the sodium hydrate aqueous solution of 3 mol/l, by solution in centrifuge with 8000rpm's
Rotating speed is centrifuged, and removes the supernatant, retains lower floor's product.
3. lower floor's solid distilled water is cleaned repeatedly, can get after wash cleanp- htclppco nanotube, with distillation
Water by its dispersed after carry out next step test.
Prepared nanotube is carried out with relevant characterization: observe its pattern using scanning electron microscope (sem) and understand
For hollow nano tubular structure, understand that the molecule of nanotube walls is by ultra-violet absorption spectrum and x-ray diffractionjAccumulation type
Arrangement mode.In addition, by infrared spectrum and x-ray power spectrum (eds) can also prove its nanotube be byp-htclppco
Composition.
2.2
Anodised aluminium (aao) template that aperture is 110 nm uses distilled water, dehydrated alcohol, acetone and chloroform etc. successively
The solvent supersonic cleaning 10min of opposed polarity, dry for standby.
1. weigh 0.010 mmolp- htclppco is dissolved in 1 ml thf (oxolane), by the aao processing
Template is immersed in the solution preparing, and suctions out remaining solution after sealing and standing 8h, vacuum drying；Mould containing aao can be obtained
Platep- htclppco nanotube.
2. dissolve aao template with the sodium hydrate aqueous solution of 3 mol/l, by solution in centrifuge with 8000rpm's
Rotating speed is centrifuged, and removes the supernatant, retains lower floor's product.
3. lower floor's solid distilled water is cleaned repeatedly, can get after wash cleanp- htclppco nanotube, with distillation
Water by its dispersed after carry out next step test.
The solid product obtaining is characterized comprehensively: result is consistent with 2.1.
2.3
Anodised aluminium (aao) template that aperture is 110 nm uses distilled water, dehydrated alcohol, acetone and chloroform etc. successively
The solvent supersonic of opposed polarity cleans 10 min, dry for standby.
1. weigh 0.010 mmolp- htclppco is dissolved in 1 ml mixed solvent, and (described mixed solvent is by dichloromethane
Form according to the volume ratio of 5:1 with methanol) in, the aao processing template is immersed in the solution preparing, sealing and standing 10
Remaining solution is suctioned out, vacuum drying after h；Can obtain containing aao templatep- htclppco nanotube.
2. dissolve aao template with the sodium hydrate aqueous solution of 3 mol/l, by solution in centrifuge with 8000rpm's
Rotating speed is centrifuged, and removes the supernatant, retains lower floor's product.
3. lower floor's solid distilled water is cleaned repeatedly, can get after wash cleanp- htclppco nanotube, with distillation
Water by its dispersed after carry out next step test.
The solid product obtaining is characterized comprehensively: result is consistent with 2.1.
2.4
Anodised aluminium (aao) template that aperture is 110 nm uses distilled water, dehydrated alcohol, acetone and chloroform etc. successively
The solvent supersonic cleaning 10min of opposed polarity, dry for standby.
1. weigh 0.005 mmolp- htclppco is dissolved in 1 ml mixed solvent, and (described mixed solvent is by dichloromethane
Form according to the volume ratio of 5:1 with methanol) in, the aao processing template is immersed in the solution preparing, sealing and standing 10
Remaining solution is suctioned out, vacuum drying after h；Can obtain containing aao templatep- htclppco nanotube.
2. dissolve aao template with the sodium hydrate aqueous solution of 3 mol/l, by solution in centrifuge with 8000rpm's
Rotating speed is centrifuged, and removes the supernatant, retains lower floor's product.
3. lower floor's solid distilled water is cleaned repeatedly, can get after wash cleanp- htclppco nanotube, with distillation
Water by its dispersed after carry out next step test.
The solid product obtaining is characterized comprehensively: result is consistent with 2.1.
Embodiment 3
1. the suprabasil interdigital electrode of ito electro-conductive glass will be etched in uses toluene, acetone, dehydrated alcohol, distilled water different successively
The solvent of polarity is cleaned by ultrasonic 3 times respectively, 5 min every time, dry for standby.
2. 1 mg embodiment 2 is preparedp- htclppco nanotube carefully uniform drop coating to dried
In the interdigital electrode of ito electro-conductive glass substrate, vacuum drying, that is, obtain the gas sensor of gas sensor.
Embodiment 4
It is built into the gas sensor that embodiment 3 preparespThe air-sensitive test device of-htclppco nanotube, for poisonous
Gas no2Air-sensitive measure.Wherein whole experiment process is to enter under fixed-bias transistor circuit between two electrodes is for 5 v and room temperature condition
Row.Using test instrunment model: Agilent b290a precision source/measuring unit.Wherein, using embodiment 2 preparationp-
The gas sensor that htclppco nanotube assembles further is carried out repeatedly to no2Air-sensitive test, result is consistent；As Figure 10-
Shown in 15.As shown in Figure 10, prepared by the present inventionp- htclppco nanotube gas sensor has the conduction property of superelevation.Figure
11 showpThe no to the 0.5-100 ppm for-htclppco nanometer tube gas sensitive sensor2There is good air-sensitive response, and
Response time and recovery time are respectively 240 s and 695 s.Figure 12 explanationp- htclppco nanometer tube gas sensitive sensor is to 100
The no of ppm2Stability preferable.Figure 13 showspAir-sensitive response (sensitivity) of-htclppco nanometer tube gas sensitive sensor
With no2Concentration has certain linear relationship.Figure 14,15 proofsp- htclppco nanometer tube gas sensitive sensor is to co and nh3Not yet
There is response, to no2There is good selectivity.In sum,p- htclppco nanometer tube gas sensitive sensor is to no2There is response
The advantages such as concentration is low, response/recovery time fast, favorable reproducibility, sensitivity is high, selectivity is strong, have in air-sensitive detection field
It is widely applied prospect.
Claims (9)
1. a kind of Metalloporphyrins, its structural formula, as shown in Equation 1:
.
2. a kind of preparation method of Metalloporphyrins described in claim 1 is it is characterised in that preparation process is as follows:
(1) under 100-110 DEG C of temperature conditionss, 5- p-hydroxybenzene -10,15,20- trichlorophenyl porphyrins and cobaltous acetate, with
N, n- dimethylformamide (dmf) be medium, with nitrogen as protective gas, stirring reaction 8-10 hour；5- p-hydroxybenzene-
The mol ratio of 10,15,20- trichlorophenyl porphyrin and cobaltous acetate is 1:7-10；
(2) it is cooled to room temperature after the completion of reacting, adds distilled water, with n, the volume ratio of n- dimethylformamide is 1:2-3, standing
1-2 h, filters, and uses distilled water and washing with alcohol respectively, obtains target productp-htclppco；
(3), in order to improve the purity of product, in step (2), products therefrom plus chloroform dissolving are tied with methanol again
Brilliant；The mol ratio of chloroform and methanol is 1:5-8.
3. a kind of Metalloporphyrins nanotube is it is characterised in that preparation process is as follows:
(1) specific solvent of metalloporphyrin described in claim 1 is dissolved, obtain the molten of 0.005 mmol ~ 0.010 mmol/ml
Liquid；Described solvent is oxolane (thf) or mixed solvent；Mixed solvent is by dichloromethane: methanol=5:1 (volume
Than) composition；
(2) anodic oxidation aluminium formwork (aao) that aperture is 110 nm is immersed in solvent prepared by step (1), sealing
Then surplus solution is removed by standing 7-10 h, and vacuum drying obtains containing aao templatep- htclppco nanotube；
(3) with the sodium hydrate aqueous solution of 3 mol/l by step (2) prepare containing aao templatep- htclppco nanotube
In aao dissolve.
4. Metalloporphyrins nanotube " and then will remain it is characterised in that its preparation process (2) according to claim 3
Keep aao motionless during remaining solution removing "；Preferably, by the way of " solution being removed with dropper ", solution is removed.
5. according to claim 3 or 4 Metalloporphyrins nanotube it is characterised in that its length be 100 μm, aperture
For 110 nm, wall thickness is 10-20 nm.
6. according to claim 5 Metalloporphyrins nanotube it is characterised in that tube wall is by the metal of plane distribution
Metalloporphyrin complexpThe nano ordered aggregation of-htclppco is constituted, and in these nanotubes, relies on intermolecular phase interaction
With that is, π-the π between porphyrin ring interacts and the effect of metal-complexing key forms orderly aggregate structure, the tube wall of nanotube
It is made up of the planar structure of orderly metalloporphyrin ring, its normal direction is axially in parallel with pipe.
7. according to claim 6 Metalloporphyrins nanotube it is characterised in that at room temperature to no2Minimum response
Concentration is 500 ppb；To 500 ppb -100 ppm no2Response time and recovery time be respectively 240 s and 695s.
8. a kind of application of Metalloporphyrins nanotube described in claim 3-7 any one is it is characterised in that be used for examining
Survey toxic gas no2Presence.
9. the gas sensor that Metalloporphyrins nanotube described in a kind of any one using claim 3-7 assembles.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109828002A (en) * | 2019-02-12 | 2019-05-31 | 中国石油大学(华东) | A kind of nitrogen dioxide gas sensitive based on four pyrenyl Cobalt Porphyrin aggregations |
| CN113773260A (en) * | 2021-08-26 | 2021-12-10 | 华南师范大学 | Covalent-like organic material and preparation method and application thereof |
| CN114487020A (en) * | 2022-02-08 | 2022-05-13 | 扬州大学 | Gas-sensitive material for lung cancer breath marker gas methanol and preparation method thereof |
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| 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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2016
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| 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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| 郑穹等: "双卟啉及其钴络合物的合成", 《武汉大学学报（自然科学版）》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109828002A (en) * | 2019-02-12 | 2019-05-31 | 中国石油大学(华东) | A kind of nitrogen dioxide gas sensitive based on four pyrenyl Cobalt Porphyrin aggregations |
| CN109828002B (en) * | 2019-02-12 | 2021-08-10 | 中国石油大学(华东) | Nitrogen dioxide gas sensitive material based on tetrapyryl porphyrin cobalt aggregate |
| 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 |
| CN114487020A (en) * | 2022-02-08 | 2022-05-13 | 扬州大学 | Gas-sensitive material for lung cancer breath marker gas methanol and preparation method thereof |
| CN114487020B (en) * | 2022-02-08 | 2023-12-22 | 扬州大学 | Gas-sensitive material for lung cancer breathing mark gas methanol and preparation method thereof |
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| CN106349248B (en) | 2018-10-23 |
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