CN106680336A - Preparation of reduced graphene oxide/zinc phthalocyanine film, and application of film in NO2 gas monitoring - Google Patents
Preparation of reduced graphene oxide/zinc phthalocyanine film, and application of film in NO2 gas monitoring Download PDFInfo
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- CN106680336A CN106680336A CN201611085254.3A CN201611085254A CN106680336A CN 106680336 A CN106680336 A CN 106680336A CN 201611085254 A CN201611085254 A CN 201611085254A CN 106680336 A CN106680336 A CN 106680336A
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- phthalocyanine zinc
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
Abstract
The invention relates to a method for adopting a reduced graphene oxide/zinc phthalocyanine film and applying the reduced graphene oxide/zinc phthalocyanine film to electrochemical monitoring of NO2. The method comprises the following steps: preparing reduced graphene oxide, preparing the reduced graphene oxide/zinc phthalocyanine film and testing the sensitivity of the NO2. The method has the beneficial effects that the preparation method of the reduced graphene oxide/zinc phthalocyanine film is simple and environmentally-friendly, and the reduced graphene oxide/zinc phthalocyanine film has high sensitivity on the NO2.
Description
Technical field
The present invention relates to a kind of adopt electrical method and be applied to fast monitored NO2, belong to electroporation and environment
Study on monitoring field.
Background technology
With the continuous development of industrial technology, many poisonous and hazardous gas can be produced in daily life and production process
Body, such as NO2；Because the gas all has very big harm to environmental and biological materials, therefore build a fast and efficiently NO2
Detection method is necessary.At present with regard to NO2The research method of sensor has a lot, but under room temperature cryogenic conditions for
Detection NO2Method still have very big challenge.There is research to point out, Graphene has unique hole network structure, larger
Specific surface area, therefore Graphene is for NO2With preferable suction-operated；Phthalocyanine Zinc as sensitive elements, due to Phthalocyanine Zinc
It is type n semiconductor material, as Phthalocyanine Zinc and oxidizing gas such as NO2When contacting with each other, it may occur that electric charge transfer, from
And pi-electron occurs delocalization and shifts in the conductive channel that π tracks are constituted, based on this electrochemical phenomena and Graphene
We construct redox graphene/Phthalocyanine Zinc composite membrane as monitoring material to characteristic, and the material is for NO2With higher
Sensitivity.
The content of the invention
It is the preparation and its application for providing a kind of redox graphene/Phthalocyanine Zinc composite membrane that the purpose of the present invention is
In monitoring NO2。
Redox graphene/Phthalocyanine Zinc the composite membrane for preparing of the present invention and its be applied to monitor NO2, bag
Include following steps：
A, preparation reduction-oxidation graphite：1mg/mL graphene oxide dispersions are prepared, by its drop coating to ito glass plate table
Face, after vacuum drying, the electrode is immersed in 0.1M phosphate buffer solutions (pH=9.3), with GO/ITO glass plates as work
Electrode, platinum plate electrode is that, to electrode, saturated calomel electrode is reference electrode, using following in the potential window of -1.5V~0.5V
Ring voltammetry redox graphene obtains redox graphene modification ito glass plate (RGO/ITO).
B, prepare redox graphene/Phthalocyanine Zinc composite membrane：Preparation include 0.12mM Phthalocyanine Zincs, in dichloromethane and four
In the mixed solution of butyl ammonium perchlorate, with RGO/ITO glass plates as working electrode, use in the potential window of 0V~1.7V
Cyclic voltammetry deposition Phthalocyanine Zinc obtains the complex film modified ito glass plates (ZnPC/RGO/ITO) of Phthalocyanine Zinc/RGO.
C, for NO2Sensitivity test：ZnPC/RGO/ITO obtained above is placed in the test system of closing, is led to
Mass flow controller (S48300/HMT) is crossed with 100sccm-1·cm-3·min-1Speed to test interior be passed through difference
The NO of concentration2Gas and high pure nitrogen gaseous mixture.Using universal meter it is tested for NO2Air-sensitive performance, the calculating of sensitivity
Formula is：S=(Ig-Ia)/Ia× 100%.IaFor the aerial current values of ZnPC/RGO/ITO, IgIt is sudden and violent for ZnPC/RGO/ITO
It is exposed at NO2Current value in gas.
Further, potential window is -1.5V~0.5V in step a.
Further, phthalocyanine zinc concentration is 0.12mM in step b.
Further, potential window is 0V~1.7V in step b.
The invention has the beneficial effects as follows：The ZnPC/RGO/ITO preparation methods for preparing are simple and environmentally-friendly, for NO2Tool
There is higher sensitivity.
Description of the drawings
Below in conjunction with the accompanying drawings the present invention is further described.
Fig. 1 is redox graphene/Phthalocyanine Zinc composite membrane (a) and Phthalocyanine Zinc film (b) for NO2Current-responsive with
NO2The relation of concentration.
Specific embodiment
Presently in connection with specific embodiment, the present invention will be further described, and following examples are intended to illustrate rather than
Limitation of the invention further.
The adsorbance of amino acid is counted as follows shown in narration in detail of the invention and examples of implementation：
S=(Ig-Ia)/Ia× 100%
S is ZnPC/RGO/ITO for NO2Sensitivity.IaFor the aerial current values of ZnPC/RGO/ITO, IgFor
ZnPC/RGO/ITO is exposed to NO2Current value in gas.
Embodiment one：
The step of preparing redox graphene/Phthalocyanine Zinc composite membrane is as follows：
(1) redox graphene is prepared：1mg/mL graphene oxide dispersions are prepared, by its drop coating to ito glass plate
Surface, after vacuum drying, the electrode is immersed in 0.1M phosphate buffer solutions (pH=9.3), with GO/ITO glass plates as work
Make electrode, platinum plate electrode is that, to electrode, saturated calomel electrode is reference electrode, is used in the potential window of -1.5V~0.5V
Cyclic voltammetry redox graphene obtains redox graphene modification ito glass plate (RGO/ITO).
(2) redox graphene/Phthalocyanine Zinc composite membrane is prepared：Preparation includes 0.12mM Phthalocyanine Zincs, in dichloromethane and
In the mixed solution of tetrabutylammonium perchlorate, with RGO/ITO glass plates as working electrode, make in the potential window of 0V~1.7V
The complex film modified ito glass plates (ZnPC/RGO/ITO) of Phthalocyanine Zinc/RGO are obtained with cyclic voltammetry deposition Phthalocyanine Zinc.
ZnPC/RGO/ITO obtained above is placed in the test system of closing, it is recorded and is not passed through NO2Gaseous mixture and
It is passed through different volumes fraction NO2The electric current of gaseous mixture is simultaneously calculated, it is found that ZnPC/RGO/ITO is 1 × 10 for volume fraction-4~1 × 10-3NO2Gaseous mixture has good sensitivity (result is as shown in Figure 1a).
Comparative example one：
Redox graphene/Phthalocyanine Zinc composite membrane and phthalocyanine film are prepared, is compared to NO2Sensitivity, as a result such as Fig. 1
It is shown, it is found that redox graphene/Phthalocyanine Zinc composite membrane is for NO2Sensitivity it is bigger, that is due to Graphene ratio
Surface area is larger, advantageously in NO2Absorption.
The redox graphene that the present invention is prepared/Phthalocyanine Zinc composite membrane, preparation process is simple, quickly.Oxygen reduction
Graphite alkene and Phthalocyanine Zinc composite are as gas sensing element for NO2With higher sensitivity, with very big
Actual application ability.
Claims (2)
1. prepare redox graphene/Phthalocyanine Zinc composite membrane and it is applied to monitor NO2, it is characterised in that：Step is as follows：
A, prepare redox graphene：1mg/mL graphene oxide dispersions are prepared, by its drop coating to ito glass plate surface,
After vacuum drying, the electrode is immersed in 0.1M phosphate buffer solutions (pH=9.3), with GO/ITO glass plates as work electricity
Pole, platinum plate electrode is that, to electrode, saturated calomel electrode is reference electrode, using circulation in the potential window of -1.5V~0.5V
Voltammetry redox graphene obtains redox graphene modification ito glass plate (RGO/ITO).
B, prepare redox graphene/Phthalocyanine Zinc composite membrane：Preparation includes 0.05~0.15mM Phthalocyanine Zincs, in dichloromethane and
In the mixed solution of tetrabutylammonium perchlorate, with RGO/ITO glass plates as working electrode, make in the potential window of 0V~1.7V
The complex film modified ito glass plates (ZnPC/RGO/ITO) of Phthalocyanine Zinc/RGO are obtained with cyclic voltammetry deposition Phthalocyanine Zinc.
C, for NO2Sensitivity test：ZnPC/RGO/ITO obtained above is placed in the test system of closing, by matter
Amount flow controller (S48300/HMT) is with 100sccm-1·cm-3·min-1Speed to test interior be passed through variable concentrations
(NO2Amount respectively from 2~30ppm) NO2Gas and high pure nitrogen gaseous mixture.Using universal meter it is tested for NO2
Air-sensitive performance, the computing formula of sensitivity is：S=(Ig-Ia)/Ia× 100%.IaIt is aerial for ZnPC/RGO/ITO
Current value, IgNO is exposed to for ZnPC/RGO/ITO2Current value in gas.
2. redox graphene/Phthalocyanine Zinc composite membrane is prepared according to claim 1 and it is applied to monitor NO2, it is special
Levying is：Phthalocyanine zinc concentration is 0.12mM in step b.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611085254.3A CN106680336B (en) | 2016-11-30 | 2016-11-30 | The preparation of redox graphene/Phthalocyanine Zinc composite membrane and its be applied to NO2Gas-monitoring |
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| CN201611085254.3A CN106680336B (en) | 2016-11-30 | 2016-11-30 | The preparation of redox graphene/Phthalocyanine Zinc composite membrane and its be applied to NO2Gas-monitoring |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030589A (en) * | 2018-07-11 | 2018-12-18 | 黑龙江工程学院 | Four-β-carboxyphenoxy metal phthalocyanine/graphene composite material and method |
| CN110208323A (en) * | 2019-05-30 | 2019-09-06 | 济南大学 | For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide |
| CN111521653A (en) * | 2020-05-06 | 2020-08-11 | 河南中医药大学 | Tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound, electrochemical sensor prepared from same and application of electrochemical sensor |
| CN114047232A (en) * | 2021-11-25 | 2022-02-15 | 长春工业大学 | Preparation method of resistance type gas sensor based on sheet-shaped composite film |
-
2016
- 2016-11-30 CN CN201611085254.3A patent/CN106680336B/en active Active
Non-Patent Citations (6)
| Title |
|---|
| CÁRDENAS-JIRÓN, LEÓN-PLATA ET AL.: "Electron Transport Properties through Graphene Oxide–Cobalt Phthalocyanine Complexes", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| COLLINS, MOHAMMED: "Gas sensitivity of some metal phthalocyanines", 《JOURNAL OF PHYSICS D: APPLIED PHYSICS》 * |
| KAROUSIS, ORTIZ ET AL.: "Zinc Phthalocyanine–Graphene Hybrid Material for Energy Conversion: Synthesis, Characterization, Photophysics, and Photoelectrochemical Cell Preparation", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| LU, OCOLA ET AL.: "Reduced graphene oxide for room-temperature gas sensors", 《NANOTECHNOLOGY》 * |
| PARK, CHOUDHURY ET AL.: "NO Adsorption on Copper Phthalocyanine Functionalized Graphite", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| ZHOU, WANG ET AL.: "Preparation, characterization and NH3-sensing properties of reduced graphene oxide/copper phthalocyanine hybrid material", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030589A (en) * | 2018-07-11 | 2018-12-18 | 黑龙江工程学院 | Four-β-carboxyphenoxy metal phthalocyanine/graphene composite material and method |
| CN109030589B (en) * | 2018-07-11 | 2020-10-02 | 黑龙江工程学院 | Tetra-beta-carboxyphenoxy metal phthalocyanine/graphene composite material and method |
| CN110208323A (en) * | 2019-05-30 | 2019-09-06 | 济南大学 | For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide |
| CN110208323B (en) * | 2019-05-30 | 2021-12-07 | 济南大学 | Organic-inorganic composite material for detecting nitrogen dioxide and gas sensor |
| CN111521653A (en) * | 2020-05-06 | 2020-08-11 | 河南中医药大学 | Tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound, electrochemical sensor prepared from same and application of electrochemical sensor |
| CN111521653B (en) * | 2020-05-06 | 2022-10-18 | 河南中医药大学 | Tetrahydroxy phthalocyanine zinc-reduced graphene oxide nano compound, electrochemical sensor prepared from same and application of electrochemical sensor |
| CN114047232A (en) * | 2021-11-25 | 2022-02-15 | 长春工业大学 | Preparation method of resistance type gas sensor based on sheet-shaped composite film |
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| Publication number | Publication date |
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| CN106680336B (en) | 2018-12-04 |
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