CN103204853B - Micrometer wire made from perylene bisimide derivatives and application of micrometer wire - Google Patents
Micrometer wire made from perylene bisimide derivatives and application of micrometer wire Download PDFInfo
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- CN103204853B CN103204853B CN201310086057.3A CN201310086057A CN103204853B CN 103204853 B CN103204853 B CN 103204853B CN 201310086057 A CN201310086057 A CN 201310086057A CN 103204853 B CN103204853 B CN 103204853B
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- diimide derivative
- perylene
- perylene diimide
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Abstract
The invention provides two biological resistive gas sensors made from perylene bisimide derivatives and a method for manufacturing the biological resistive gas sensors. Perylene of the biological resistive gas sensors contains different substituting groups. Source regions and drain regions of the sensors are made from elementary gold; channel regions of the sensors comprise single micrometer wires or nanowires made from two types of perylene bisimide derivatives; and gate dielectric layers of the sensors are made from silicon and silicon dioxide. The biological gas sensors made from the two types of perylene bisimide derivatives are high in sensitivity when in hydrazine hydrate atmosphere, and variation of the sensitivity of each sensor is closely related to molecular structures. The biological resistive gas sensors and the method have the advantages that the hydrazine hydrate atmosphere can be efficiently and quickly detected, the sensors are simple in structure and small in size, and are portable, and the biological resistive gas sensors and the method have a high application prospect in amine gas detection.
Description
Technical field
The present invention relates to a kind of Organic Electricity resistive gas sensor, the efficient quick being especially suitable for hydrazine hydrate atmosphere detects.
Background technology
In recent years, along with industrial production development, people's living standard improve day by day, environmental problem also becomes increasingly conspicuous.Have report when gas fuel burning and toxic gas incident of leakage, environmental quality and general health problem have caused the extensive concern of society.Given this, the gas sensor of Study and Development excellent performance has become the top priority of related scientific research personnel.Particularly in the last few years, the development of nanomaterials and nanotechnology and progress, greatly advance the Synthesis and applications development of Novel air dependent sensor.The gas sensor with nanostructure developed at present can be used for detecting multiple gases, as CO, H
2and the inflammable gas such as Sweet natural gas, and H
2s, NO
x, NH
3with toxic gases such as hydrocarbon polymers, be widely used in multiple fields such as industrial monitoring, weather monitoring, indoor-outdoor air quality monitoring and medical treatment.But, up to this point, about the research of gas sensor mainly concentrates on inorganic nanostructures material, the applied research of organic nanostructure material on gas sensor is still more delayed, and organic nanostructure sensor is owing to having, and service temperature is low, power consumption is little, cost is low, preparation method is easy and received increasing concern in recent years with advantages such as microelectronic industry matched well.
Perylene diimide derivative is as a class N-shaped organic semiconductor, because it has the constitutional features of electron deficiency, therefore comparatively responsive to giving the amine gas of electronics, can be used for preparing the gas sensor detecting such gas.Although the research of perylene diimide derivative gas sensor obtains tremendous development over a little Nian of Jin, but its performance study still also exists following deficiency: 1) research work at present mainly concentrates on the fluorescent type gas sensor relying on its optical property to change, and relatively lag behind based on the resistance-type gas sensor research of its semiconductor property, this is unfavorable for its miniaturization, is more unfavorable for that gas efficient quick detects; 2) Gas-sensing measurment is lower, limits its application in real life; 3) lack systematicness for the design of gas sensor research perylene diimide derivative molecular, the relation of molecular structure and its sensing capabilities is not elaborated yet.Therefore, further develop and there is higher sensitivity perylene diimide derivative resistance-type gas sensor, and the relation of Jie Shi perylene diimide derivative molecular structure and sensing capabilities has become one of problem demanding prompt solution in its gas sensing performance study process.
The rapid emergence of perylene diimide derivative preparation means is that the development of its resistance-type gas sensor provides new power, and in conjunction with advanced micro-processing technology, the resistance-type gas sensor of many Ji Yu perylene diimide derivative dimension micro-nano structures is used widely.Er perylene diimide derivative gas sensor structure activity relationship announcement, enrich its preparation further theoretical, will the fast development of Tui Dong perylene diimide derivative resistance-type gas sensor further.
Summary of the invention
Technical problem to be solved by this invention detects for toxic and harmful efficient quick, provides Yi Zhong perylene diimide derivative resistance-type gas sensor.
The single micro wire of San Zhong perylene diimide derivative or nano wire are made into gas sensor by the present invention, when it is placed in 10 ppm hydrazine hydrate gases, gas molecule Jiang Yu perylene diimide derivative generation transfer transport, cause gas sensor resistance that the change of the 2-3 order of magnitude occurs within 3-5 second, realize the detection to specific gas, and the change of Jie He perylene diimide derivative molecular structure, realize the regulation and control to its resistance-type gas sensor sensitivity.
Accompanying drawing explanation
Fig. 1 is PTCDI-CN
2c
10nuclear magnetic spectrogram.
Fig. 2 is PTCDI-Cl
4c
10nuclear magnetic spectrogram.
Fig. 3 is PTCDI-CN
2c
10the SEM figure of gas sensor.
Fig. 4 is PTCDI-Cl
4c
10the SEM figure of gas sensor.
Fig. 5 is PTCDI-CN
2c
10the electrical resistance time variation diagram of gas sensor.
Fig. 6 is PTCDI-Cl
4c
10the electrical resistance time variation diagram of gas sensor.
Embodiment
embodiment 1:
The preparation method of Suo Shu perylene diimide derivative:
1)
n, N 'bromo-3,4:9, the 10-perylene diimides of-bis-(3,7-dimethyl octyl group) perylene-1,7-bis-(0.50 g, 0.6 mmol) dissolves in 25 mL with 0.81 g hydrogenation is cuprous
n, N '-dimethyl formamide, stirs 6 hours in 150 oC under nitrogen protection, and add 150 mL water subsequently, stirring is spent the night, suction filtration, dry, and silicagel column is separated (eluent is chloroform) and obtains 0.35 g
n, N '-bis-(3,7-dimethyl octyl group) perylene-1,7-dicyano-3,4:9,10-perylene diimides (PTCDI-CN
2c
10), productive rate 81.2%.
1H NMR (CDCl
3):
δ9.70 (d,
J= 8.0 Hz, 2H), 8.98 (s, 2H), 8.94 (d,
J= 8.0 Hz, 2H), 4.27 (t,
J=10.8 Hz, 4H), 1.56-0.86 (m, 38H). MALDI-MS: 720.9 (calcd.721.9). Anal. Calcd for C
46H
48N
4O
4: C, 76.64; H, 6.71; N, 7.77; Found: C, 75.85; H, 6.72; N, 8.12.
2) 1,6,7,10-tetra-chloro-3,4,9,10-perylenetetracarboxylic dianhydrides (0.60 g, 1.14 mmol) and 2.0 g salt of wormwood, 2.4 g potassiumiodides dissolve in 25 mL
n-methyl-2-pyrrolidone; stir 1 hour in 80 oC under nitrogen protection, add bromo-3,7-dimethyl octane (0.796 g of 1-; 3.60 mmol); continue reaction after 2 hours, be cooled to room temperature, add the mixed solvent (volume ratio is 1:3) of 300 mL hydrochloric acid (2 M) and methyl alcohol subsequently; stirring is spent the night; suction filtration, dry, silicagel column is separated (eluent is chloroform) and obtains 0.68 g
n, N 'chloro-3,4,9, the 10-perylene diimides (PTCDI-Cl of-bis-(3,7-dimethyl octyl group) perylene-1,6,7,10-tetra-
4c
10), productive rate 73.9%.
1H NMR (CDCl
3):
δ8.61 (s, 4H), 4.27 (t,
J= 8.0 Hz, 4H), 1.50-0.88 (m, 38H). MALDI-MS: 808.7 (calcd.808.6). Anal. Calcd for C
44H
46Cl
4N
2O
4: C, 65.35; H,5.73; N, 3.46; Found: C, 65.12; H, 5.25; N, 3.73.
embodiment 2:
The micron of Ji Yu Shang Shu perylene diimide derivative and the preparation method of nano wire:
1) by 0.3 mL PTCDI-CN
2c
10chloroformic solution (1 mg.mL
-1) capacity of being transferred to is in the weighing bottle of 10 mL, adds 0.9 mL chloroform and 1.8 mL methyl alcohol subsequently, vibrate after 10 minutes and leave standstill after 24 hours, obtain reddish brown precipitation, be characterized by diameter 0.4-2 μm micro wire through scanning electron microscope.
2) by 0.4 mL PTCDI-Cl
4c
10chloroformic solution (1 mg.mL
-1) capacity of being transferred to is in the weighing bottle of 10 mL, adds 0.1 mL chloroform and 3.0 mL methyl alcohol subsequently, vibrate after 10 minutes and leave standstill after 12 hours, obtain reddish brown precipitation, be characterized by diameter 1-3 μm micro wire through scanning electron microscope.
embodiment 3:
The micron of Ji Yu Shang Shu perylene diimide derivative and the application of nano wire:
1) by PTCDI-CN
2c
10micro wire is scattered in methyl alcohol, drips to be applied to deposit on the silicon chip of silicon-dioxide, after solvent in atmosphere volatile dry, selects 2-3 μm of micro wire as mask, in 5 × 10
-5in Torr vacuum systems, be about 50 nm layer gold with 0.5/s deposition rate, subsequently mask removed, obtain PTCDI-CN
2c
10the detecting electrode of gas sensor.
Detecting electrode after completing is put into the airtight vacuum metal chamber that volume is about 2 L, this system is directly connected with vacuum pump, treats this vacuum systems Pressure Drop to 10
-4during pa, electrode is connected with Keithley 4200-SCS electrical detection system, the PTCDI-CN of record vacuum systems
2c
10resistance (R
0), by microsyringe, the hydrazine hydrate of 2 μ L is injected cavity subsequently, record PTCDI-CN
2c
10resistance (R) curve over time, further by analysis R/R
0change curve in time, obtains PTCDI-CN
2c
10the sensitivity of gas sensor under hydrazine hydrate atmosphere.
2) by PTCDI-Cl
4c
10micro wire is scattered in methyl alcohol, drips to be applied to deposit on the silicon chip of silicon-dioxide, after solvent in atmosphere volatile dry, selects 1-2 μm of micro wire as mask, in 5 × 10
-5in Torr vacuum systems, be about 50 nm layer gold with 0.5/s deposition rate, subsequently mask removed, obtain PTCDI-Cl
4c
10the detecting electrode of gas sensor.
Detecting electrode after completing is put into the airtight vacuum metal chamber that volume is about 2 L, this system is directly connected with vacuum pump, treats this vacuum systems Pressure Drop to 10
-4during pa, electrode is connected with Keithley 4200-SCS electrical detection system, the PTCDI-Cl of record vacuum systems
4c
10resistance (R
0), by microsyringe, the hydrazine hydrate of 2 μ L is injected cavity subsequently, record PTCDI-Cl
4c
10resistance (R) curve over time, further by analysis R/ R
0change curve in time, obtains PTCDI-Cl
4c
10the sensitivity of gas sensor under hydrazine hydrate atmosphere.
The efficient quick that the present invention not only achieves lower concentration hydrazine hydrate gas detects, and achieves the regulation and control sensitive to sensor by the change of molecular structure, and structure is simple, volume is little, be easy to carry, and is with a wide range of applications in amine gas detection.
Although the present invention discloses as above with several preferred embodiment; but it is not for limiting the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; change arbitrarily when doing or equivalently to replace, therefore protection scope of the present invention is as the criterion when the protection model defined with the claim of enclosing.
Claims (3)
1. cyano substituent perylene diimide derivative is contained in Yi Zhong perylene gulf, and it is the compound that structural formula represents as follows that Qi Te levies Yu perylene diimide derivative:
2. one kind according to claim 1 state micro wire or nano wire prepared by perylene diimide derivative, it is characterized in that Gai perylene diimide derivative of Yi is raw material, obtained in chloroform and methanol mixed solution by dilute solution precipitated crystal method, its preparation process is as follows: be 0.3mL by volume, concentration is 1mg.mL
-1it is in the weighing bottle of 10mL that the chloroformic solution of perylene diimide derivative is transferred to capacity, adds 0.9mL chloroform and 1.8mL methyl alcohol subsequently, vibrates after 10 minutes and leaves standstill 24 hours, obtain micro wire or the nano wire of Xiang Ying perylene diimide derivative.
3. as claim 2 state the micro wire of perylene diimide derivative or an application for nano wire, it is characterized in that, realize the detection of hydrazine hydrate atmosphere as gas sensor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310086057.3A CN103204853B (en) | 2013-03-18 | 2013-03-18 | Micrometer wire made from perylene bisimide derivatives and application of micrometer wire |
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|---|---|---|---|
| CN201310086057.3A CN103204853B (en) | 2013-03-18 | 2013-03-18 | Micrometer wire made from perylene bisimide derivatives and application of micrometer wire |
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| CN103204853B true CN103204853B (en) | 2015-02-25 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910728B (en) * | 2014-02-25 | 2016-05-11 | 中国科学院化学研究所 | The laser of monodispersity responds one dimension organic semiconductor micro belt of photic movement and its preparation method and application |
| CN104262396B (en) * | 2014-09-10 | 2016-05-25 | 天津理工大学 | Position, a kind of gulf gold replaces perylene diimides derivative |
| CN106565801B (en) * | 2016-10-26 | 2018-11-16 | 河南大学 | It is a kind of containing α-pyranoside imide derivative and its preparation method and application |
| CN107098904B (en) * | 2017-06-07 | 2019-05-31 | 河南大学 | A kind of gulf 1,7- imide derivatives containing nitro and its application in ammonia detection |
| CN107363267B (en) * | 2017-07-03 | 2019-02-01 | 燕山大学 | A method of the direct-reduction metal ion based on diimide derivative as electronic transmission mediums |
| CN108003157B (en) * | 2017-12-19 | 2023-07-28 | 山东省医学科学院药物研究所 | Perylene diimide compound, synthesis method thereof and Fe thereof 3+ Application in detection |
| CN110283173B (en) * | 2019-07-09 | 2021-11-16 | 济南大学 | Perylene bisimide compound and preparation method and application thereof |
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Inventor after: Huang Yongwei Inventor after: Li Chunli Inventor after: Li Hui Inventor after: Fu Lina Inventor after: Zhai Haiyan Inventor before: Huang Yongwei Inventor before: Li Chunli Inventor before: Wang Junchao Inventor before: Zhang Weiguang Inventor before: Li Hui |
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Free format text: CORRECT: INVENTOR; FROM: HUANG YONGWEI LI CHUNLI WANG JUNCHAO ZHANG WEIGUANG LI HUI TO: HUANG YONGWEI LI CHUNLI LI HUI FU LINA ZHAI HAIYAN |
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