CN109626367A - Graphene composite material, preparation method and applications - Google Patents
Graphene composite material, preparation method and applications Download PDFInfo
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- CN109626367A CN109626367A CN201910013096.8A CN201910013096A CN109626367A CN 109626367 A CN109626367 A CN 109626367A CN 201910013096 A CN201910013096 A CN 201910013096A CN 109626367 A CN109626367 A CN 109626367A
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract
The embodiment of the invention discloses a kind of preparation methods of graphene composite material, the following steps are included: zinc nitrate hexahydrate, cetyl trimethylammonium bromide solution are mixed at room temperature, methylimidazole aqueous solution is added dropwise while stirring, nitrogen-doped graphene dispersion liquid is instilled in above-mentioned solution, hydro-thermal reaction is carried out to get the nitrogen-doped graphene composite material of load ZIF-8.The embodiment of the present invention synthesizes ZIF-8/ nitrogen-doped graphene composite material by the way that ZIF-8 to be carried on nitrogen-doped graphene by hydro-thermal.Pass through influencing each other between ZIF-8 and nitrogen-doped graphene, so as to avoid the reunion of ZIF-8/ nitrogen-doped graphene composite material, the adsorption capacity of ZIF-8/ nitrogen-doped graphene composite material is improved, to improve the extraction ability of ZIF-8/ nitrogen-doped graphene composite material.
Description
Technical field
The present embodiments relate to grapheme material field, in particular to a kind of graphene composite material, preparation method and
It is applied.
Background technique
Environment incretion interferent (Endocrine disrupting chemicals, EDCs), also known as environmental hormone.People
For example persistent organic chloride pesticide of chemical environment hormone, steroids, detergent, plasticizer that work synthesizes etc. are widely present in
In production and living.These hormones are penetrated into soil and water source by effluent sewage or rubbish etc., and are entered in organism, interference life
The synthesis and metabolism of object and human body internal hormone, to influence reproduction, nerve, the function of immune system or even carcinogenic, this direct shadow
Ring the procreation survival and development for arriving the mankind.Therefore, focus concerned by people is increasingly becoming to the monitoring of EDCs in soil and water source.
Although EDCs is widely present in environment, usual content is low (often with μ gL- 1Or ngL- 1Meter), it is difficult to directly examined using instrument
It surveys, or by complex matrices interference is difficult to judge and accurate quantitative analysis.Thus it is badly in need of selective good and high sensitivity the EDCs of development
Separation/enrichment and analysis method are remained, to provide relatively reliable effective monitoring data.
Currently used for separate with enrichment environment in EDCs method there are many kinds of, specifically include solid phase extraction, solid phase
The certain methods such as microextraction method, liquid-liquid extraction method, liquid-liquid micro-extraction method, cloud point extraction method.And solid phase extraction is more mature, tool
Have the advantages that easy to operate, at low cost.Graphene has good adsorptivity, thermal stability, chemical stability and high-ratio surface
Product, is often used in solid extracting agent, to realize that different substrates Gold Samples category ion, pesticide, drug, biological sample wait
Survey the separation and enrichment of object.But the graphene of the Hummers method preparation of graphene is commonly prepared, thickness, size, shape are not
Easy to control, irreversible reunion easily occurs for laminated structure, this can hinder effective absorption of analyte and desorption, reduces test analyte
Selectivity the problems such as, to limit its research and application in separation and concentration.
Summary of the invention
The embodiment of the present invention is designed to provide a kind of graphene composite material, preparation method and applications, avoids stone
The reunion of black alkene composite material, improves the adsorption capacity of graphene composite material, to improve graphene composite material
Extraction ability.
In order to solve the above technical problems, the embodiment provides a kind of preparation method of graphene composite material,
The following steps are included:
Zinc nitrate hexahydrate, cetyl trimethylammonium bromide solution are mixed at room temperature, two are added dropwise while stirring
Methylimidazole aqueous solution instills nitrogen-doped graphene dispersion liquid in above-mentioned solution, carries out hydro-thermal reaction to get load ZIF-8
Nitrogen-doped graphene composite material.
The embodiments of the present invention also provide a kind of stones that the preparation method by above-mentioned graphene composite material is prepared
Black alkene composite material.
The embodiments of the present invention also provide above-mentioned graphene composite material answering on Solid Phase Extraction environmental disturbances hormone
With.
In terms of existing technologies, ZIF-8 is carried on nitrogen by hydro-thermal and mixed the embodiment of the present invention by the embodiment of the present invention
On miscellaneous graphene, ZIF-8/ nitrogen-doped graphene composite material is synthesized.Pass through the mutual shadow between ZIF-8 and nitrogen-doped graphene
It rings, it may be assumed that
(1) porosity, selectivity and adsorption capacity of ZIF-8 can be improved in nitrogen-doped graphene；
(2) oxygen-containing functional group at nitrogen-doped graphene edge plays knot to the synthesis of ZIF-8/ nitrogen-doped graphene composite material
The effect of structure directed agents；
(3) stability of ZIF-8 can be improved as support frame for nitrogen-doped graphene；
(4) ZIF-8 material can be embedded in nitrogen-doped graphene, effectively avoid the reunion of nitrogen-doped graphene.
So as to avoid the reunion of ZIF-8/ nitrogen-doped graphene composite material, it is multiple to improve ZIF-8/ nitrogen-doped graphene
The adsorption capacity of condensation material, to improve the extraction ability of ZIF-8/ nitrogen-doped graphene composite material.
In addition, the preparation method of ZIF-8/ nitrogen-doped graphene composite material the following steps are included: by zinc nitrate hexahydrate,
Cetyl trimethylammonium bromide solution is mixed at room temperature, methylimidazole aqueous solution is added dropwise while stirring, by N doping
Graphene dispersing solution instills in above-mentioned solution, and hydro-thermal reaction is up to ZIF-8/ nitrogen-doped graphene composite material.
In addition, the preparation method of nitrogen-doped graphene is the following steps are included: that polyethyleneimine is slowly dropped into cyanuric acid is molten
In liquid, ultrasound obtains clear solution to clarifying；Melamine solution is added into clear solution, water bath with thermostatic control reaction is laggard
The processing of row suction filtration, obtains precursor polymer nanometer sheet powder after dry；Presoma nanometer sheet powder is placed in nitrogen atmosphere
Under tube furnace calcined to get nitrogen-doped graphene.
In addition, the reaction condition that tube furnace is calcined is to maintain 2h from room temperature to 450 DEG C, then heat to 500
1h is maintained after~800 DEG C, heating rate is 2.3 DEG C/min.
In addition, the condition of water bath with thermostatic control reaction is the time 3~5 hours, keeping temperature is 30 DEG C.
In addition, the condition of hydro-thermal reaction is 120 DEG C of temperature, the reaction time is 2~6h.
In addition, the method for Solid Phase Extraction environmental disturbances hormone includes the following steps: to fill out 5~25mg graphene composite material
It is charged in solid-phase extraction column, the bisphenol-A solution of 25~250mL is subjected to extraction processing by solid-phase extraction column, using eluant, eluent
Solid-phase extraction column is eluted, the Solid Phase Extraction to environmental disturbances hormone in solution is completed.
In addition, eluant, eluent is selected from any one of methanol, acetone, acetonitrile, ethyl acetate, chloroform.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment, the element in attached drawing with same reference numbers label are expressed as similar element, remove
Non- to have special statement, composition does not limit the figure in attached drawing.
Fig. 1 a is the SEM figure of the nitrogen-doped graphene in the embodiment of the present invention 1；
Fig. 1 b is the SEM figure of the ZIF-8 in the embodiment of the present invention 1；
Fig. 1 c is the TEM figure of the ZIF-8/ nitrogen-doped graphene composite material in the embodiment of the present invention 1；
Fig. 1 d is nitrogen-doped graphene, ZIF-8, ZIF-8/ nitrogen-doped graphene composite material in the embodiment of the present invention 1
X-ray diffractogram；
Fig. 2 is shadow of the dosage to effect of extracting of the ZIF-8/ nitrogen-doped graphene composite material in the embodiment of the present invention
It rings；
Fig. 3 be in the embodiment of the present invention bisphenol-A liquor capacity to ZIF-8/ nitrogen-doped graphene composite material Solid Phase Extraction
The influence of pillar enrichment multiplying power；
Fig. 4 is that the pH value of bisphenol-A solution in the embodiment of the present invention extracts ZIF-8/ nitrogen-doped graphene composite material solid phase
Take the influence of pillar extraction efficiency；
Fig. 5 be in the embodiment of the present invention eluant, eluent type to ZIF-8/ nitrogen-doped graphene composite material solid phase extraction column
It is enriched with the influence of multiplying power.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with attached drawing to the present invention
Each embodiment be explained in detail.However, it will be understood by those skilled in the art that in various embodiments of the present invention
In, in order to make the reader understand this application better, many technical details are proposed.But even if without these technical details and
Based on the various changes and modifications of following embodiment, the application technical solution claimed also may be implemented.
Embodiment 1
The embodiment of the present invention 1 is related to a kind of preparation method of graphene composite material, comprising the following steps:
(1) it the preparation of nitrogen-doped graphene: weighs 1.04g cyanuric acid and is placed in 150mL conical flask, 40mL water is added to shake
It is even.Polyethyleneimine (molecular weight 1800) is added dropwise in conical flask (about 5-6 drop), ultrasonic dissolution 20min.If solid is long in bottle
Time does not dissolve and then adds a few drop polyethyleneimines, until clarification.0.6g melamine (C is added into centrifuge tube3H6N6), add
Water 8ml oscillation shakes up.It is transferred into conical flask, washs 1-2 times.Conical flask 3~5min of ultrasound adds water about to 80mL.Cone
Shape bottle closure filters after 30 DEG C of 3~5h of oscillation, secondary water washing in constant temperature oscillator, and vacuum oven is dry, obtains forerunner
Body nanometer sheet PEI-MCA powder.Take appropriate presoma nanometer sheet PEI-MCA powder under conditions of logical nitrogen in vacuum tube furnace
Interior calcination, tube furnace keep 2h first from room temperature to 450 DEG C.Then 1h, heating rate are kept after being warming up to 500~800 DEG C
It is 2.3 DEG C/min, the substance being collected into is nitrogen-doped graphene；
(2) preparation of ZIF-8/ nitrogen-doped graphene composite material: take 10mg nitrogen-doped graphene ultrasonic disperse in 10mL
It is spare in methanol.Take the zinc nitrate hexahydrate aqueous solution of 6mL 0.0336M and the cetyl trimethyl bromination of 0.1mL 0.1M
5min is mixed in ammonium salt solution (CTAB) at room temperature.Add the water-soluble liquid chamber of methylimidazole of the 10mL 1.096M now matched
Temperature is lower to stir 5min, and the nitrogen-doped graphene in step 1 is 4 hours ultrasonic in methyl alcohol, obtains nitrogen-doped graphene dispersion liquid,
Then dispersion liquid is slowly added dropwise while stirring into above-mentioned solution, 5min is stirred in continuation at room temperature.It is transferred in reaction kettle, 120
2~6h is reacted at DEG C.Centrifugation, methanol washing.Gained final product is after grinding after being dried in vacuo at 60 DEG C of the product being collected into
ZIF-8/ nitrogen-doped graphene composite material.
Embodiment 2
It verifies ZIF-8 and whether generates ZIF-8/ nitrogen-doped graphene composite material with reacting for nitrogen-doped graphene
As shown in figure Fig. 1 a~1d, the SEM figure (a) of nitrogen-doped graphene that the embodiment of the present invention 1 is prepared, ZIF-8
SEM schemes the TEM figure (c) and nitrogen-doped graphene, ZIF-8, ZIF-8/ nitrogen of (b), ZIF-8/ nitrogen-doped graphene composite material
The X-ray diffractogram (d) of doped graphene composite material.By Fig. 1 a~1d it is found that can learn that ZIF-8 is successfully supported on nitrogen and mixes
Miscellaneous graphene surface.
Embodiment 3
Influence of the material utilization amount of ZIF-8/ nitrogen-doped graphene composite material to effect of extracting
The ZIF-8/ nitrogen-doped graphene composite material being prepared in embodiment 1 is on Solid Phase Extraction environmental disturbances hormone
Application, concrete application method is as follows:
By 5,10,15,20, the ZIF-8/ nitrogen-doped graphene composite material of 25mg be loaded on 1mL Solid Phase Extraction void column respectively
In, up and down plus PE sieve plate is to prevent material to be lost in extraction process.The solid phase extraction column prepared is connected to solid phase extraction
Instrument is taken, first uses 5mL secondary distilled water, then activated by solid phase extraction column to it with 5mL methanol.Then by 1mg/L's
The bisphenol-A solution of 100mL with given pace by be equipped with ZIF-8/ nitrogen-doped graphene composite material solid phase extraction column, it is double
Phenol A is enriched in solid phase extraction column, then methanol is selected to elute solid phase extraction column, eluent is collected for surveying
It is fixed.
Influence of the material utilization amount to effect of extracting, as a result as shown in Fig. 2, as shown in Figure 2, in ZIF-8/ nitrogen-doped graphene
When composite material is 10mg~25mg, fluorescence intensity is no longer with the increase liter of ZIF-8/ nitrogen-doped graphene composite material dosage
Height illustrates that the complete absorption to bisphenol-A may be implemented in the ZIF-8/ nitrogen-doped graphene composite material of 10mg.Therefore, solid phase extracts
Usage amount of drawing materials selects 10mg.
Embodiment 4
Bisphenol-A solution optimal volume is selected
By the ZIF-8/ nitrogen-doped graphene composite material of 10mg loaded in 1mL Solid Phase Extraction void column, add PE sieve plate up and down
To prevent material to be lost in extraction process.The solid phase extraction column prepared is connected to solid-phase extracting instrument, is first used 5mL bis- times
Distilled water, then it is activated by solid phase extraction column with 5mL methanol.Then by the 25 of 1mg/L, 50,100,250mL
Bisphenol-A solution passes through the solid phase extraction column equipped with ZIF-8/ nitrogen-doped graphene composite material, bisphenol-A respectively with given pace
It is enriched in solid phase extraction column, then methanol is selected to elute solid phase extraction column, eluent is collected for measuring.
Influence of the liquor capacity to enrichment multiplying power, as a result as shown in figure 3, from the figure 3, it may be seen that being 100mL in bisphenol-A solution
When, the enrichment multiplying power highest of bisphenol-A solution.
Embodiment 5
Influence of the pH value of bisphenol-A solution to extraction efficiency
The ZIF-8/ nitrogen-doped graphene composite material of 10mg is loaded on respectively in 1mL Solid Phase Extraction void column, up and down plus PE
Sieve plate is to prevent material to be lost in extraction process.The solid phase extraction column prepared is connected to solid-phase extracting instrument, first uses 5mL
Secondary distilled water, then it is activated by solid phase extraction column with 5mL methanol.Be then 2 by the 100mLpH value of 1mg/L,
3,4,5,6,7,8,9,10,11 bisphenol-A solution is respectively with given pace by being equipped with ZIF-8/ nitrogen-doped graphene composite wood
The solid phase extraction column of material, bisphenol-A are enriched in solid phase extraction column, then methanol are selected to wash solid phase extraction column
De-, eluent is collected for measuring.
Influence of the pH value to extraction efficiency, as a result as shown in figure 4, as shown in Figure 4, pH value on Solid Phase Extraction efficiency influence compared with
It is small.Therefore experimentation is no longer adjusted pH value.
Embodiment 6
Best eluant, eluent is selected
The ZIF-8/ nitrogen-doped graphene composite material of 10mg is loaded on respectively in 1mL Solid Phase Extraction void column, up and down plus PE
Sieve plate is to prevent material to be lost in extraction process.The solid phase extraction column prepared is connected to solid-phase extracting instrument, first uses 5mL
Secondary distilled water, then it is activated by solid phase extraction column with 5mL methanol.Then the 100mL bisphenol-A of 1mg/L is molten
Respectively with given pace by the solid phase extraction column equipped with ZIF-8/ nitrogen-doped graphene composite material, bisphenol-A is enriched with liquid
In solid phase extraction column, then methanol, acetone, acetonitrile, ethyl acetate, chloroform is selected to wash solid phase extraction column
De-, eluent is collected for measuring.
Influence of the eluant, eluent type to enrichment multiplying power, as a result as shown in figure 5, as shown in Figure 5, when eluant, eluent is methanol,
The enrichment multiplying power highest of bisphenol-A solution.
It will be understood by those skilled in the art that the various embodiments described above are realization specific embodiments of the present invention, and
In practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (9)
1. a kind of preparation method of graphene composite material, which comprises the following steps:
Zinc nitrate hexahydrate, cetyl trimethylammonium bromide solution are mixed at room temperature, dimethyl is added dropwise while stirring
Imidazoles aqueous solution instills nitrogen-doped graphene dispersion liquid in above-mentioned solution, carries out hydro-thermal reaction to get the nitrogen of load ZIF-8
Doped graphene composite material.
2. the preparation method of graphene composite material according to claim 1, which is characterized in that the nitrogen-doped graphene
Preparation method the following steps are included:
Polyethyleneimine is slowly dropped into cyanuric acid solution, ultrasound obtains clear solution to clarifying；
Melamine solution is added into the clear solution, suction filtration processing is carried out after water bath with thermostatic control reaction, is obtained after dry
Precursor polymer nanometer sheet powder；
The tube furnace that the presoma nanometer sheet powder is placed under nitrogen atmosphere is calcined to get nitrogen-doped graphene.
3. the preparation method of graphene composite material according to claim 2, which is characterized in that the tube furnace is forged
The reaction condition of burning is to be warming up to 450 DEG C, maintains 2h, 1h, heating rate 2.3 are maintained after being then warming up to 500~800 DEG C again
℃/min。
4. the preparation method of graphene composite material according to claim 3, which is characterized in that the water bath with thermostatic control reaction
Condition be the time 3~5 hours, keep temperature be 30 DEG C.
5. the preparation method of graphene composite material according to any one of claims 1 to 4, which is characterized in that the water
The condition of thermal response is 120 DEG C of temperature, and the reaction time is 2~6h.
6. a kind of graphene that the preparation method by the described in any item graphene composite materials of Claims 1 to 5 is prepared
Composite material.
7. application of the graphene composite material as claimed in claim 6 on Solid Phase Extraction environmental disturbances hormone.
8. application of the graphene composite material according to claim 7 on Solid Phase Extraction environmental disturbances hormone, feature
It is, the method for the Solid Phase Extraction environmental disturbances hormone includes the following steps:
5~25mg graphene composite material is filled into solid-phase extraction column, the bisphenol-A solution of 25~250mL is passed through described
Solid-phase extraction column carries out extraction processing, is eluted using eluant, eluent to solid-phase extraction column, completes to swash environmental disturbances in solution
The Solid Phase Extraction of element.
9. application of the graphene composite material according to claim 8 on Solid Phase Extraction environmental disturbances hormone, feature
It is, the eluant, eluent is selected from any one of methanol, acetone, acetonitrile, ethyl acetate, chloroform.
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| CN111272840A (en) * | 2020-02-21 | 2020-06-12 | 衡阳师范学院 | Cu-MOFs loaded nitrogen-doped graphene composite material and preparation method and application thereof |
| CN111393950A (en) * | 2020-04-22 | 2020-07-10 | 中国科学院山西煤炭化学研究所 | Graphene anti-corrosion primer for heat exchanger in marine environment and preparation method thereof |
| CN112500795A (en) * | 2020-10-23 | 2021-03-16 | 福建比美特环保集团有限公司 | Preparation process of wall covering with formaldehyde removing function |
| CN112642402A (en) * | 2021-01-11 | 2021-04-13 | 北京工业大学 | Preparation method of MOF-C composite material for removing phosphate in sewage |
| CN113460993A (en) * | 2021-06-29 | 2021-10-01 | 湘潭大学 | Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery |
| CN113979431A (en) * | 2021-11-01 | 2022-01-28 | 电子科技大学 | Method for auxiliary transfer of graphene by supporting framework/adhesive composite structure |
| CN114496586A (en) * | 2022-02-18 | 2022-05-13 | 常州大学 | Nitrogen-doped three-dimensional graphene/MOF (Metal organic framework) derived carbon composite electrode material for capacitive deionization and preparation and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111272840A (en) * | 2020-02-21 | 2020-06-12 | 衡阳师范学院 | Cu-MOFs loaded nitrogen-doped graphene composite material and preparation method and application thereof |
| CN111272840B (en) * | 2020-02-21 | 2023-01-06 | 衡阳师范学院 | Cu-MOFs loaded nitrogen-doped graphene composite material and preparation method and application thereof |
| CN111393950A (en) * | 2020-04-22 | 2020-07-10 | 中国科学院山西煤炭化学研究所 | Graphene anti-corrosion primer for heat exchanger in marine environment and preparation method thereof |
| CN112500795A (en) * | 2020-10-23 | 2021-03-16 | 福建比美特环保集团有限公司 | Preparation process of wall covering with formaldehyde removing function |
| CN112500795B (en) * | 2020-10-23 | 2023-10-03 | 福建比美特环保集团有限公司 | Preparation process of wall clothing with formaldehyde removal function |
| CN112642402A (en) * | 2021-01-11 | 2021-04-13 | 北京工业大学 | Preparation method of MOF-C composite material for removing phosphate in sewage |
| CN113460993A (en) * | 2021-06-29 | 2021-10-01 | 湘潭大学 | Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery |
| CN113460993B (en) * | 2021-06-29 | 2022-07-05 | 湘潭大学 | Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery |
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