CN110451491A - A kind of preparation method of porous graphene granular materials - Google Patents
A kind of preparation method of porous graphene granular materials Download PDFInfo
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- CN110451491A CN110451491A CN201910771883.9A CN201910771883A CN110451491A CN 110451491 A CN110451491 A CN 110451491A CN 201910771883 A CN201910771883 A CN 201910771883A CN 110451491 A CN110451491 A CN 110451491A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
Abstract
The present invention discloses a kind of preparation method of porous graphene granular materials, comprising: prepares the mixed aqueous solution of graphene oxide/polyvinyl alcohol, wherein 5~15mg/mL of graphene oxide concentration, the concentration of polyvinyl alcohol is 5~150mg/mL；Graphene oxide/polyvinyl alcohol mixture aqueous solution is poured into the hydro-thermal container for being placed with cellular board, hydrothermal reduction processing is carried out, obtains the graphene/polyvinyl alcohol hydrogel being filled in honeycomb；It is freeze-dried the graphene/polyvinyl alcohol hydrogel being filled in cellular board, forms the graphene/polyvinyl alcohol aeroge being filled in cellular board；Graphene/polyvinyl alcohol aeroge is separated with cellular board, obtains graphene/polyvinyl alcohol aerogel particle, high temperature reduction processing is carried out to graphene/polyvinyl alcohol aerogel particle, obtains porous graphene granular materials.Method of the invention can be effectively removed the polyvinyl alcohol of addition by high-temperature heat treatment.Simple process, high production efficiency.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of preparation method of porous graphene granular materials.
Background technique
Porous material is that pollutant process commonly filters and adsorbent material.Since porous graphene material has superelevation
Specific surface area and surface-active, the porosity of super large and loose surface texture, in water process, air cleaning, catalyst carrier
Equal depollutions of environment field has great application value.
In practical application scene, it is often required that porous material be graininess, could play to greatest extent its filtering and
The effect of absorption.For carbonaceous material, it usually needs the additives such as addition adhesive, auxiliary agent are just able to achieve stable structure
Honeycombed grain material, but additive can destroy the structure of porous material to a certain extent, and remaining additive also can
Hole is blocked, to reduce the excellent properties of honeycombed grain material, and the size of honeycombed grain material is inconsistent and size is difficult
With control.
Summary of the invention
In view of the above situation of the prior art, the object of the present invention is to provide a kind of preparations of porous graphene granular materials
Method.The present invention can be effectively removed the polyvinyl alcohol of addition by high-temperature heat treatment, and form that density is low, specific surface area
Height, filter capacity are brilliant, oil suction is hydrophobic, the porous graphene granular materials of antibiotic and sterilizing, excellent in mechanical performance.
Above-mentioned purpose of the invention is realized using following technical scheme:
A kind of preparation method of porous graphene granular materials, comprising the following steps:
Step 1: preparing the mixed aqueous solution of graphene oxide and polyvinyl alcohol, and in mixed aqueous solution, graphene oxide is dense
5~15mg/mL is spent, the concentration of polyvinyl alcohol is 5~150mg/mL.Specifically, the oxidation including 1.1,5~15mg/mL of preparation
Graphene aqueous solution, and be ultrasonically treated, wherein the ultrasonic treatment is that 20~25kHz is ultrasonically treated, 5~30min of time.
The graphene oxide by improving the preparation of Hummers method can be used in graphene oxide；1.2, it then at 95~99 DEG C of temperature, and stirs
In the case where, a certain amount of polyvinyl alcohol is added into graphene oxide water solution, deionized water is replenished in time in whipping process
Amount, it is ensured that graphene oxide concentration is identical in step 1.1 in final mixture aqueous solution, and the concentration of polyvinyl alcohol for 5~
150mg/mL can make graphene oxide be uniformly dispersed, final products large specific surface area, and voidage is high.Wherein the stirring is machine
Tool stirring, revolving speed are 200~400rpm, and 2~10h of mixing time, the degree of hydrolysis of polyvinyl alcohol is 95~99%.
Step 2: the hydrothermal reduction processing of graphene oxide/polyvinyl alcohol mixed aqueous solution forms graphene/polyethylene
Alcohol hydrogel, comprising: cellular board is placed in water heating kettle, and graphene oxide/polyvinyl alcohol mixture aqueous solution is poured into water
In hot kettle, at 160~200 DEG C, hydro-thermal reaction 12~for 24 hours, it is cooled to room temperature, the graphene that acquisition is filled in honeycomb/poly-
Polyvinyl alcohol hydrogel.
By adjusting the specification of cellular board, the graphene particles material that size is consistent and size is controllable can get.Honeycomb
Plate can be the plastic materials cellular boards such as metal materials cellular board or PC, PP such as aluminum honeycomb panel, iron cellular board, but be not limited to above
The type.The honeycomb hole shape of cellular board is not limited to hexagon, can be round, rectangle and triangle.Cellular board is in hydro-thermal
Modes of emplacement in kettle is unrestricted, cellular direction can be it is vertical or horizontal, depend on convenience.
Step 3: freeze-drying hydrothermal reduction treated graphene/polyvinyl alcohol hydrogel forms graphene/poly- second
Enol aeroge；Tool ground, is placed in freeze drying equipment for the graphene being filled in cellular board/polyvinyl alcohol hydrogel product
In, the graphene/polyvinyl alcohol aeroge being filled in cellular board is formed after dry.Freeze-drying is vacuum freeze drying, temperature
Degree is -50~-15 DEG C, vacuum degree < 10Pa, and the time is 2~5 days.
Step 4: the processing of graphene/polyvinyl alcohol aeroge high temperature reduction, including by graphene/polyvinyl alcohol airsetting
Glue is separated with cellular board, column graphene/polyvinyl alcohol aerogel particle is obtained, to column graphene/polyvinyl alcohol aeroge
Particle carries out high temperature reduction processing, obtains porous graphene granular materials.Wherein the high temperature reduction processing includes by chimney rock
30~60min of constant temperature after black alkene/polyvinyl alcohol aerogel particle is warming up to 600~1500 DEG C under the conditions of anaerobic or few oxygen, with
Cooled to room temperature afterwards.In temperature-rise period, heating rate is not higher than 5 DEG C/min, keeps the temperature in 100~120 DEG C of temperature ranges
No less than 30min, and heat preservation is no less than 30min at 200 DEG C.By the way that in temperature-rise period, control heating rate is not higher than 5
DEG C/min, it is no less than 30min in 100~120 DEG C of temperature range heat preservations, and heat preservation is no less than 30min at 200 DEG C, can have
Effect control graphene/polyvinyl alcohol aerogel particle rate of reduction, avoids that violent reduction reaction occurs and causes breakage of particles
And it crushes.
Compared with prior art, the present invention has following technical effect:
1, for the present invention using polyvinyl alcohol as adhesive, solution viscosity is low, and viscosity is still after mixing with graphene
It is very low, it is easy to produce.In addition, the polyvinyl alcohol of addition can be effectively removed by high-temperature heat treatment.
2, porous graphene granular materials prepared by the present invention, is all made of graphene, and has good structure strong
Degree, particle size uniformity is controllable, and specific surface area is high, filter capacity is brilliant, oil suction is hydrophobic, antibiotic and sterilizing, excellent in mechanical performance, fits
Close a variety of depollution of environment application fields.
3, present invention process method is simple, production efficiency improves, and can directly prepare that mechanical strength is good, table using existing equipment
The high porous material of face activity.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo of the porous graphene granular materials prepared in embodiment 1.
Fig. 2 is scanning electron microscope (SEM) photo of the porous graphene granular materials prepared in embodiment 3.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
5min is ultrasonically treated using the graphene oxide water solution 100ml, 20kHz that deionized water prepares 10mg/mL.Oxidation
The graphene oxide by improving the preparation of Hummers method can be used in graphene.It is water-soluble to graphene oxide under the conditions of 97 DEG C of oil baths
The polyvinyl alcohol 3g that addition degree of hydrolysis is 99% in liquid, mechanical stirring 4 hours, revolving speed 300rpm, and deionization is replenished in time
Water.Final mixture aqueous solution 100mL is obtained, wherein graphene oxide concentration is 10mg/mL, and the concentration of polyvinyl alcohol is
30mg/mL。
Hexagon aluminum honeycomb panel is flat on to the bottom of water heating kettle, by graphene oxide/polyvinyl alcohol mixture aqueous solution
It pours into water heating kettle, and mixture aqueous solution liquid level is consistent with the height of aluminum honeycomb panel.Hydrothermal reaction condition: temperature is 180 DEG C,
Time is for 24 hours.After water heating kettle is cooled to room temperature, the graphene/polyvinyl alcohol hydrogel being filled in aluminum honeycomb panel is obtained.
The graphene being filled in aluminum honeycomb panel/polyvinyl alcohol hydrogel product is placed in freeze drying equipment, it is dry
Graphene/polyvinyl alcohol the aeroge being filled in aluminum honeycomb panel is formed afterwards.Freeze-drying be vacuum freeze drying, temperature be-
35 DEG C, vacuum degree < 10Pa, the time is 3 days.
Graphene/polyvinyl alcohol aeroge is separated with aluminum honeycomb panel, obtains hexagonal cylindrical graphene/polyvinyl alcohol gas
Gel particle, and be put into Muffle furnace, the constant temperature 60min after anaerobic or few oxygen condition are warming up to 800 DEG C is then naturally cold
But to room temperature.In temperature-rise period, heating rate is 5 DEG C/min, keeps the temperature 30min in 100~120 DEG C of temperature ranges, and 200
30min is kept the temperature at DEG C.Obtaining product is porous graphene granular materials.Fig. 1 is the porous graphene prepared in the present embodiment
Scanning electron microscope (SEM) photo of granular materials.
The material all has excellent adsorption capacity to all kinds of organic liquids, the gasoline of absorbable 150 times of own wt,
190 times of toluene, 183 times of ethyl alcohol and 194 times of hexamethylene.
Embodiment 2
The difference from embodiment 1 is that the concentration of polyvinyl alcohol is 20mg/mL in mixture aqueous solution 100mL.It obtains
Porous graphene granular materials is similar to Example 1 to the adsorption capacity of all kinds of organic liquids, in addition, its antibiotic rate is tested,
Antibiotic rate (staphylococcus aureus) is 93%.
Embodiment 3
The difference from embodiment 1 is that the temperature of high temperature reduction is 1000 DEG C.The porous graphene granular materials pair of acquisition
The adsorption capacity of all kinds of organic liquids is similar to Example 1, in addition, the absorption property of its PARA FORMALDEHYDE PRILLS(91,95) is tested, the suction of PARA FORMALDEHYDE PRILLS(91,95)
Attached amount is 210mg/g, the filterability granular materials that can be used in air purifier.Fig. 2 is the porous stone prepared in the present embodiment
Scanning electron microscope (SEM) photo of black alkene granular materials.
Embodiment 4
Difference with embodiment 3 is that the concentration of polyvinyl alcohol in mixture aqueous solution 100mL is 20mg/mL.It obtains
Porous graphene granular materials is similar to Example 1 to the adsorption capacity of all kinds of organic liquids, in addition, testing it to aqueous solution
In 96% methylene blue adsorption capacity, methylene blue adsorption number amount be 1017mg/g.
Embodiment 5
Difference with embodiment 4 is that the temperature of high temperature reduction is 1100 DEG C.The porous graphene granular materials pair of acquisition
The adsorption capacity of all kinds of organic liquids is similar to Example 1, and after burning, and still has 80% oil absorption capacity.
Embodiment 6
The difference from embodiment 1 is that the temperature of high temperature reduction is 900 DEG C.The porous graphene granular materials of acquisition is to each
The adsorption capacity of class organic liquid is similar to Example 1.
The density of the porous graphene granular materials of embodiment 1-6 is 40mg/cm3Left and right.
Claims (9)
1. a kind of preparation method of porous graphene granular materials, includes the following steps:
Step 1: preparing the mixed aqueous solution of graphene oxide/polyvinyl alcohol, in mixed aqueous solution, graphene oxide concentration 5~
15mg/mL, the concentration of polyvinyl alcohol are 5~150mg/mL；
Step 2: graphene oxide/polyvinyl alcohol mixture aqueous solution is poured into the hydro-thermal container for being placed with cellular board, is carried out
Hydrothermal reduction processing, obtains the graphene/polyvinyl alcohol hydrogel being filled in honeycomb；
Step 3: graphene/polyvinyl alcohol hydrogel that freeze-drying is filled in cellular board, formation are filled in cellular board
Graphene/polyvinyl alcohol aeroge；
Step 4: graphene/polyvinyl alcohol aeroge is separated with cellular board, obtains graphene/polyvinyl alcohol aerogel particle,
High temperature reduction processing then is carried out to graphene/polyvinyl alcohol aerogel particle, obtains porous graphene granular materials.
2. preparation method described in accordance with the claim 1, wherein the step 1 includes the graphite oxide of 5~15mg/mL of preparation
Then aqueous solution is ultrasonically treated；In the case where 95~99 DEG C of temperature and stirring, add into graphene oxide water solution
Enter polyvinyl alcohol, deionized water is replenished in time, it is ensured that graphene oxide concentration in graphene oxide/polyvinyl alcohol mixed aqueous solution
It remains unchanged, and the concentration of polyvinyl alcohol is 5~150mg/mL.
3. preparation method according to claim 2, wherein the ultrasonic treatment is that 20~25kHz is ultrasonically treated, the time 5~
30min。
4. preparation method according to claim 2, wherein the stirring uses mechanical stirring, revolving speed is 200~400rpm,
2~10h of mixing time.
5. preparation method described in accordance with the claim 1, wherein hydrothermal reduction processing is included at 160~200 DEG C, hydro-thermal
Reaction 12~for 24 hours, it then cools to room temperature.
6. preparation method described in accordance with the claim 1, wherein high temperature reduction processing includes by graphene/polyvinyl alcohol gas
Gel particle is warming up to 600~1500 DEG C under the conditions of anaerobic or few oxygen, and keeps the temperature 30~60min, cooled to room temperature.
7. preparation method according to claim 6, wherein heating rate is not higher than 5 DEG C/min, In in temperature-rise period
100~120 DEG C of temperature range heat preservation is no less than 30min, and heat preservation is no less than 30min at 200 DEG C.
8. according to the method for claim 1, wherein the graphene oxide is using the oxidation for improving the preparation of Hummers method
Graphene.
9. temperature is -50~-15 according to the method for claim 1, wherein the freeze-drying is vacuum freeze drying
DEG C, vacuum degree < 10Pa, the time is 2~5 days.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113999425A (en) * | 2021-11-15 | 2022-02-01 | 福州大学 | Preparation method and application of super-hydrophobic graphene/polyvinyl alcohol aerogel |
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Application publication date: 20191115 |