CN108264638B - Synthesis method of polynaphthylamine-loaded graphene - Google Patents
Synthesis method of polynaphthylamine-loaded graphene Download PDFInfo
- Publication number
- CN108264638B CN108264638B CN201810287975.5A CN201810287975A CN108264638B CN 108264638 B CN108264638 B CN 108264638B CN 201810287975 A CN201810287975 A CN 201810287975A CN 108264638 B CN108264638 B CN 108264638B
- Authority
- CN
- China
- Prior art keywords
- loaded graphene
- polynaphthylamine
- synthesizing
- sol
- polynaphthalene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Carbon And Carbon Compounds (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention belongs to the technical field of material chemistry, and relates to a method for synthesizing polynaphthalene amine loaded graphene. According to the method, polynaphthylamine is uniformly modified on graphene oxide in an in-situ polymerization mode, and then the surface groups of the graphene oxide are removed through electron beam irradiation, so that the uniform modification of the polynaphthylamine on the surface of the graphene is realized. The synthesized polynaphthylamine-loaded graphene has good sensitivity to benzene series gas.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and relates to a method for synthesizing polynaphthalene amine loaded graphene.
Background
The structure of the polynaphthylamine is as follows:
the conjugated polymer is a conjugated polymer with a condensed ring structure, and has certain application prospect in the fields of anticorrosive coatings, electrocatalysis, electrochromism, electrochemical sensors, gas sensors and the like. The polynaphthylamine has low conductivity, the conductivity can be greatly improved by modifying the polynaphthylamine on the graphene, and the sensitivity of the sensor can be effectively improved by the synergistic effect of the conjugated structure of the polynaphthylamine and the pi-pi conjugated molecular chain of the graphene. However, the graphene material has poor dispersibility in various solvents, and uniform modification of in-situ polymerization is difficult to realize.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of polynaphthalene amine loaded graphene. The method comprises the following steps:
(1) adding naphthylamine monomer and graphite oxide into acidic aqueous solution, carrying out ultrasonic dispersion to obtain purple brown sol, namely sol A, dissolving an oxidant into the acidic aqueous solution, slowly dropwise adding the oxidant into the sol A to obtain mixed sol,
(2) putting the mixed sol obtained in the step (1) into a heat preservation device, stirring at constant temperature, and reacting to obtain black precipitate;
(3) washing and drying the black precipitate obtained in the step (2) to obtain an intermediate product, namely polynaphthalene amine loaded graphene oxide powder;
(4) and (3) performing electron beam irradiation on the obtained powder to obtain the final product of polynaphthylamine-loaded graphene powder.
The addition amount of the graphite oxide is 0.2-1.5 gL-1(ii) a The ultrasonic dispersion time is 1-2 h, and the concentration of the naphthylamine monomer in the mixed sol is 0.1-0.5 mol L-1(ii) a The pH of the acidic aqueous solution is less than 2.
The oxidant comprises one or a combination of ammonium persulfate, potassium persulfate, sodium persulfate and ferric trichloride, and the molar ratio of the oxidant to the naphthylamine monomer is 1: 1-3: 1.
The continuous stirring reaction time is 12-24 hours, and the temperature is room temperature-60 ℃.
The washing is alternately washing by using deionized water and ethanol, filtering is carried out by adopting a centrifuge precipitation or suction filtration device after each washing, a filtered product is dispersed in the deionized water or the ethanol again, the filtering is repeated until the pH value of the filtrate is 7, and the final washing by using the ethanol is convenient for drying; the drying is carried out in a vacuum oven at 50-80 ℃, and the vacuum degree is less than 133 Pa.
The irradiation dose of the electron beam is 30-160 kGy.
According to the method, polynaphthylamine is uniformly modified on graphene oxide in an in-situ polymerization mode, and then the surface groups of the graphene oxide are removed through electron beam irradiation, so that the uniform modification of the polynaphthylamine on the surface of the graphene is realized. In addition, the trapezoidal conjugated structure of the polynaphthylamine ensures better radiation stability and thermal stability, and is not depolymerized in the irradiation process. The synthesized polynaphthylamine-loaded graphene has good sensitivity to benzene series gas.
The disclosure and features of the invention have been disclosed above, however the invention as described above relates only briefly or in particular part to the invention which may be characterised by a better sensitivity to benzene-based gases than the synthetic polynaphthylamine-loaded graphene. The disclosure herein relates more. Therefore, the scope of the present invention should not be limited to the disclosure of the embodiments, but should include all combinations of the contents embodied in different parts, and various substitutions and modifications without departing from the present invention, and are covered by the claims of the present invention.
Drawings
Fig. 1 is a TEM photograph of a case where polynaphthylamine-supported graphene was synthesized using the present invention (example 1).
Detailed Description
Example 1
(1) 0.01mol of naphthylamine monomer and 0.02g of graphite oxide are added into 50mL of acidic aqueous solution, ultrasonic dispersion is carried out for 2h to obtain purple brown sol (sol A), 0.03mol of ammonium persulfate is dissolved into 50mL of acidic aqueous solution, and the mixture sol is slowly dripped into the sol A to obtain mixed sol.
(2) Putting the mixed sol obtained in the step (1) into a 60 ℃ heat preservation device, stirring at constant temperature, and reacting for 24 hours to obtain black precipitate;
(3) washing the black precipitate obtained in the step (2) with deionized water and ethanol alternately, filtering the black precipitate by using a centrifuge precipitation or suction filtration device after each washing, dispersing the filtered product in the deionized water or ethanol again, repeatedly filtering until the pH value of the filtrate is 7, and drying the filtrate in a vacuum oven at 50 ℃ to obtain an intermediate product, namely the polynaphthylamine-loaded graphene oxide powder;
(4) the obtained powder is subjected to 160kGy electron beam irradiation to obtain a final product, namely polynaphthylamine-loaded graphene powder, and a TEM photograph is shown in FIG. 1. The polynaphthylamine is uniformly and tightly loaded on the graphene sheets.
The obtained powder is dispersed and coated on a six-pin ceramic tube gas-sensitive test element, and a WS-30A type gas-sensitive element test system is adopted to test the response of the gas-sensitive element to 30 percent toluene/70 percent xylene mixed gas under different concentrations. The sensitivity of 1ppm 30% toluene/70% xylene gas mixture was 8.9. The requirement of gas-sensitive sensing is met.
Examples 2 and 3
For comparison:
example 1 above was repeated, without addition of graphite oxide, to give a powder of polynaphthalene, with a sensitivity of 1ppm 30% toluene/70% xylene gas mixture of 1.4.
The above example 1 was repeated without electron beam irradiation to obtain a powder of polynaphthylamine-supported graphene oxide having a sensitivity of 1.41.9 at 1ppm 30% toluene/70% xylene mixed gas.
The comparative samples all responded much less to the benzene series than example 1.
Example 4
(1) 0.05mol of naphthylamine monomer and 0.15g of graphite oxide are added into 50mL of acidic aqueous solution, ultrasonic dispersion is carried out for 2h to obtain purple brown sol (sol A), 0.05mol of potassium persulfate is dissolved into 50mL of acidic aqueous solution, and the mixture is slowly dripped into the sol A to obtain mixed sol.
(2) Stirring the mixed sol obtained in the step (1) at a constant temperature at room temperature for reacting for 16 hours to obtain black precipitate;
(3) washing the black precipitate obtained in the step (2) with deionized water and ethanol alternately, filtering the black precipitate by using a centrifuge precipitation or suction filtration device after each washing, dispersing the filtered product in the deionized water or ethanol again, repeatedly filtering until the pH value of the filtrate is 7, and drying the filtrate in a vacuum oven at 80 ℃ to obtain an intermediate product, namely polynaphthylamine-loaded graphene oxide powder;
(4) and (3) carrying out 100kGy electron beam irradiation on the obtained powder to obtain the final product of polynaphthylamine-loaded graphene powder.
The obtained powder is dispersed and coated on a six-pin ceramic tube gas-sensitive test element, and a WS-30A type gas-sensitive element test system is adopted to test the response of the gas-sensitive element to 30 percent toluene/70 percent xylene mixed gas under different concentrations. The sensitivity of 1ppm 30% toluene/70% xylene gas mixture was 11.5.
Example 5
(1) 0.02mol of naphthylamine monomer and 0.1g of graphite oxide are added into 50mL of acidic aqueous solution, ultrasonic dispersion is carried out for 2h to obtain purple brown sol (sol A), 0.04mol of sodium persulfate is dissolved into 50mL of acidic aqueous solution, and the mixture is slowly dripped into the sol A to obtain mixed sol.
(2) Stirring the mixed sol obtained in the step (1) at a constant temperature at room temperature for reaction for 12 hours to obtain black precipitate;
(3) washing the black precipitate obtained in the step (2) with deionized water and ethanol alternately, filtering the black precipitate by using a centrifuge precipitation or suction filtration device after each washing, dispersing the filtered product in the deionized water or ethanol again, repeatedly filtering until the pH value of the filtrate is 7, and drying the filtrate in a vacuum oven at 50 ℃ to obtain an intermediate product, namely the polynaphthylamine-loaded graphene oxide powder;
(4) and (3) carrying out 30kGy electron beam irradiation on the obtained powder to obtain the final product of polynaphthylamine-loaded graphene powder.
The sensitivity of 1ppm 30% toluene/70% xylene gas mixture was 5.7.
Example 6
(1) 0.03mol of naphthylamine monomer and 0.1g of graphite oxide are added into 50mL of acidic aqueous solution, ultrasonic dispersion is carried out for 2h to obtain purple brown sol (sol A), 0.05mol of ferric trichloride is dissolved into 50mL of acidic aqueous solution, and the mixture is slowly dripped into the sol A to obtain mixed sol.
(2) Putting the mixed sol obtained in the step (1) into a 50 ℃ heat preservation device, stirring at constant temperature, and reacting for 18 hours to obtain black precipitate;
(3) washing the black precipitate obtained in the step (2) with deionized water and ethanol alternately, filtering the black precipitate by using a centrifuge precipitation or suction filtration device after each washing, dispersing the filtered product in the deionized water or ethanol again, repeatedly filtering until the pH value of the filtrate is 7, and drying the filtrate in a vacuum oven at 60 ℃ to obtain an intermediate product, namely polynaphthylamine-loaded graphene oxide powder;
(4) and (3) carrying out 80kGy electron beam irradiation on the obtained powder to obtain the final product of polynaphthylamine-loaded graphene powder.
The sensitivity of 1ppm 30% toluene/70% xylene gas mixture was 7.1.
Claims (7)
1. A method for synthesizing poly (naphthylamine) loaded graphene is characterized by comprising the following steps:
(1) adding naphthylamine monomer and graphite oxide into acidic aqueous solution, carrying out ultrasonic dispersion to obtain purple brown sol, namely sol A, dissolving an oxidant into the acidic aqueous solution, slowly dropwise adding the oxidant into the sol A to obtain mixed sol,
(2) putting the mixed sol obtained in the step (1) into a heat preservation device, stirring at constant temperature, and reacting to obtain black precipitate;
(3) washing and drying the black precipitate obtained in the step (2) to obtain an intermediate product, namely polynaphthalene amine loaded graphene oxide powder;
(4) and (3) performing electron beam irradiation on the obtained powder to obtain the final product of polynaphthylamine-loaded graphene powder.
2. According to the rightThe method for synthesizing the polynaphthalene amine loaded graphene according to claim 1, which is characterized in that: the addition amount of the graphite oxide is 0.2-1.5 gL-1(ii) a The ultrasonic dispersion time is 1-2 h, and the concentration of the naphthylamine monomer in the mixed sol is 0.1-0.5 mol L-1(ii) a The pH of the acidic aqueous solution is less than 2.
3. The method for synthesizing the polynaphthalene amine loaded graphene according to claim 1, characterized in that: the oxidant comprises one or a combination of ammonium persulfate, potassium persulfate, sodium persulfate and ferric trichloride, and the molar ratio of the oxidant to the naphthylamine monomer is 1: 1-3: 1.
4. The method for synthesizing polynaphthalene-loaded graphene according to claim 1, characterized in that: the reaction time of the constant-temperature stirring reaction is 12-24 hours, and the temperature is room temperature-60 ℃.
5. The method for synthesizing polynaphthalene-loaded graphene according to claim 1, characterized in that: the washing is alternately washing by using deionized water and ethanol, filtering is carried out by adopting a centrifuge precipitation or suction filtration device after each washing, a filtered product is dispersed in the deionized water or the ethanol again, the filtering is repeated until the pH value of the filtrate is 7, and the final washing by using the ethanol is convenient for drying; the drying is carried out in a vacuum oven at 50-80 ℃, and the vacuum degree is less than 133 Pa.
6. The method for synthesizing polynaphthalene-loaded graphene according to claim 1, characterized in that: the irradiation dose of the electron beam is 30-160 kGy.
7. Polynaphthylamine-loaded graphene prepared by the method for synthesizing polynaphthylamine-loaded graphene according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810287975.5A CN108264638B (en) | 2018-03-26 | 2018-03-26 | Synthesis method of polynaphthylamine-loaded graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810287975.5A CN108264638B (en) | 2018-03-26 | 2018-03-26 | Synthesis method of polynaphthylamine-loaded graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108264638A CN108264638A (en) | 2018-07-10 |
| CN108264638B true CN108264638B (en) | 2020-09-15 |
Family
ID=62777506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810287975.5A Active CN108264638B (en) | 2018-03-26 | 2018-03-26 | Synthesis method of polynaphthylamine-loaded graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108264638B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906065A (en) * | 2018-07-02 | 2018-11-30 | 合肥萃励新材料科技有限公司 | A kind of Nd doping LaFeO3The preparation method of nano particle |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772702B (en) * | 2012-10-18 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of poly-naphthalidine nano hollow structure and preparation method thereof |
| CN103897183B (en) * | 2014-04-02 | 2016-04-06 | 电子科技大学 | Binary carbon material-conductive composite nano-polymers air-sensitive film and preparation method thereof |
| CN104448306B (en) * | 2014-12-09 | 2016-09-28 | 湖南科技大学 | A kind of preparation method and its usage of poly-1,8 naphthylenediamine grafted graphene oxides |
| CN104891476B (en) * | 2015-05-12 | 2017-02-01 | 上海大学 | Electron beam irradiation method for preparation of nitrogen-doped reducing graphene |
| CN104889417B (en) * | 2015-05-12 | 2016-08-10 | 上海大学 | The method of electron beam irradiation synthesizing nano-silver/reduced graphene composite |
| CN104910378B (en) * | 2015-05-26 | 2017-06-06 | 浙江理工大学 | A kind of polyaniline/graphene oxide nano composite material preparation method |
| US9718935B1 (en) * | 2016-04-20 | 2017-08-01 | Eastman Kodak Company | Method of preparing article with polyaniline pattern |
| CN106280439A (en) * | 2016-08-16 | 2017-01-04 | 曹健 | The preparation of a kind of graphene-polyaniline composite material and method |
-
2018
- 2018-03-26 CN CN201810287975.5A patent/CN108264638B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108264638A (en) | 2018-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108362750B (en) | Preparation method of gold nanoparticle-doped covalent organic framework-based composite material electrode | |
| Song et al. | Polymer carbon dots—a highlight reviewing their unique structure, bright emission and probable photoluminescence mechanism | |
| Ayad et al. | Chitosan/polyaniline nanofibers coating on the quartz crystal microbalance electrode for gas sensing | |
| KR101612514B1 (en) | Process for preparing carbon quantum dots using emulsion | |
| CN108398468B (en) | Preparation method of carbon paste electrode modified based on covalent organic framework material | |
| CN108884109B (en) | Metal-organic hybrid structures built with multidirectional polydentate ligands | |
| Rabiee et al. | Ultra-sensitive electrochemical on-line determination of Clarithromycin based on Poly (L-Aspartic acid)/graphite oxide/pristine graphene/glassy carbon electrode | |
| CN109071466B (en) | Multidentate ligands for metal-organic hybrid structures | |
| Liu et al. | Novel fluorescent sensor using molecularly imprinted silica microsphere‐coated CdSe@ CdS quantum dots and its application in the detection of 2, 4, 6‐trichlorophenol from environmental water samples | |
| CN108264638B (en) | Synthesis method of polynaphthylamine-loaded graphene | |
| Bian et al. | Nanocomposites based on rutile-TiO2 and polyaniline | |
| Dawn et al. | Preparation of size-controlled, highly populated, stable, and nearly monodispersed Ag nanoparticles in an organic medium from a simple interfacial redox process using a conducting polymer | |
| CN108728078B (en) | Preparation method and application of NaYF4 Gd/Tm/Er @ CdTe | |
| CN113086970B (en) | Method for simply preparing temperature-resistant salt-tolerant carbon dots | |
| CN110818840B (en) | Synthesis method of polysaccharide biomass-based rapid self-repairing gel | |
| CN103772702B (en) | A kind of poly-naphthalidine nano hollow structure and preparation method thereof | |
| Ramalingam et al. | SYNTHESIS, SURFACE AND TEXTURAL CHARACTERIZATION OF Ag DOPED POLYANILINE-SiO 2 (Pan-Ag/RHA) NANOCOMPOSITESDERIVEDFROM BIOMASS MATERIALS. | |
| Mavundla et al. | Synthesis and Characterization of Novel Nanophase Hexagonal Poly (2, 5‐dimethoxyaniline) | |
| Wang et al. | Covalent Organic Framework/Graphene Hybrids: Synthesis, Properties, and Applications | |
| Casa et al. | Synthesis and characterization of water stable ZnO quantum dots based-sensor for nitro-organic compounds | |
| Yu et al. | Synthesis of glycidyl ether of poly (bisphenol-A 1, 1′-ferrocene dicarboxylate) and its electrochemical behavior | |
| Khozemy | Radiation synthesis of gas sensor based on polyaniline nanoflake-poly vinyl alcohol) film for four hazardous gases (NH3, CO2, H2S and phenol) | |
| CN110551291B (en) | Porous interpenetrating zinc-organic supramolecular polymer and preparation method and application thereof | |
| Huang et al. | Aggregation kinetics and precipitation phenomena in poly (phenylisocyanide) | |
| CN109181683B (en) | Calcium-metal-based organic framework material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |