CN107051404A - A kind of hydrophobic adsorbent based on graphene oxide - Google Patents
A kind of hydrophobic adsorbent based on graphene oxide Download PDFInfo
- Publication number
- CN107051404A CN107051404A CN201710224088.9A CN201710224088A CN107051404A CN 107051404 A CN107051404 A CN 107051404A CN 201710224088 A CN201710224088 A CN 201710224088A CN 107051404 A CN107051404 A CN 107051404A
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- Prior art keywords
- graphene oxide
- hydrophobic adsorbent
- modified
- preparation
- crosslinking agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of hydrophobic adsorbent based on graphene oxide.The hydrophobic adsorbent of the three-dimensional graphene oxide of specially a kind of fluorochemical and its and to the adsorption applications of methylene blue dye.The method that innovative proposition of the invention is modified using fluorochemical monomer to graphene oxide, the report being modified currently without fluorochemical monomer to graphene oxide.Modified graphene oxide foam bulk multi-hole obtained by the present invention, specific surface area is big, and density is low and Stability Analysis of Structures, and preparation process is simple, easy to control.
Description
Technical field
The present invention relates to a kind of hydrophobic adsorbent based on graphene oxide, specially a kind of graphene oxide/fluorine-containing
The preparation method of compound composite material (modified graphene oxide foam), belongs to technical field of inorganic.
Background technology
Graphene is a kind of new material for the individual layer laminated structure being made up of carbon atom, is most thin two found at present
Tie up material.At present, the preparation method of graphene mainly has：Micromechanics stripping method, epitaxial growth method, chemical vapor deposition (CVD)
Method, graphite oxide reducing process and carbon nanometer transformation approach etc..Compared with two dimensional crystal graphene, modified three-dimensional graphene oxide
With the specific surface area and activity higher compared with two-dimensional graphene.With, high adsorption capacity bigger than surface, high mechanical strength, it is easy to
The good characteristics such as preparation, these unique properties cause modified graphene oxide sponge sorbing material to turn into environmental pollution treatment
Focus.
Dyestuff is main water pollution material, from industries such as printing, weaving, printing and dyeing and papermaking.Most dyestuff
Molecular structure complexity is stable, it is difficult to biodegradable.The active charcoal of traditional adsorbent, resin, polyurethane foam, mineral and its useless
Gurry.Regenerating active carbon is difficult, and processing cost is higher, therefore application surface is narrow, is typically only used at the relatively low waste water from dyestuff of concentration
Reason；Resin adsorption is using less, cost height；Polyurethane foam is generally used in heavy metal wastewater thereby, water there being phenol etc. in oil slick, water
Organic pollutants are adsorbed, to waste water from dyestuff using less；Mineral and its discarded object absorption are easily introduced heavy metal ion, cause secondary dirt
Dye.
The content of the invention
The purpose of invention be to provide with the hydrophobic adsorbent of the three-dimensional graphene oxide of fluorochemical a kind of and its
And to the adsorption applications of methylene blue dye.The vapor that the present invention is prepared has specific surface area big, Stability Analysis of Structures, absorption property
Good advantage, its preparation method process is simple, it is easy to operate.
The present invention is to be realized by the following technical programs：
A kind of three-dimensional graphene oxide structure material, is aoxidized using crosslinking agent and fluorochemical monomer to the three-dimensional prepared
Graphene is modified experiment.
In the preferred embodiments of the invention, described preparation method comprises the following steps：
1) preparation method of graphene oxide：Raw material native graphite is taken, sodium nitrate, potassium permanganate and the concentrated sulfuric acid exist respectively
Stirring completes oxidation experiment in ice bath (3 DEG C -8 DEG C) and oil bath (35 DEG C -98 DEG C)；
2) separating-purifying：By above-mentioned mixed liquor by centrifuge 5-7 times, dialysed to pH value of solution connect with bag filter afterwards
Weakly acidic pH；
3) preparation of modified graphene oxide：Crosslinking agent function amide-type monomer and fluorine-containing list are added into above-mentioned mixed liquor
Body, in 50-80 DEG C of oil bath reaction 2-8h；
4) freeze-drying of modified graphene oxide：By step 3) mixed liquor ultrasound after 30-60 minutes, be fixed on mould
In, it is put into freeze drying box and is freeze-dried, prepares the modified graphene oxide foam i.e. present invention and be based on graphite oxide
The hydrophobic adsorbent of alkene.
Step 1) in, the mass ratio of native graphite and potassium permanganate is controlled 1:3~1:6.
Step 2) in the bag filter scale that uses be MD34 (8000-14000).
Step 3) described in crosslinking agent be NMA, fluorochemical monomer is hexafluoroisopropanol.
Step 3) in dosage of crosslinking agent be graphene oxide quality 2%~6%, preferably 3%~5%；Fluorochemical monomer
Consumption is equal with the quality of graphene oxide.
Step 4) drying time be 48h~72h.
The larger graphene oxide synusia of specific surface area and its mutually entanglement in modified graphene sponge prepared by the present invention
The complicated network structure formed can play good filtration for the water soluble organic dye molecule in water, can
It is used as a kind of efficient sorbing material.Specific adsorption process is as follows：
Adsorb methylene blue solution：Take out step 4) modified graphene oxide foam in mould, being put into concentration is
In 0.05g/L~0.1g/L methylene blue solution, the absorbance of different periods is determined, solution is dense when drawing absorbance minimum
Degree, calculates adsorption capacity.
The beneficial effects of the invention are as follows：
1st, the innovative crosslinking agent by methyl nitrosourea class of the present invention is modified for graphene oxide, currently without amide-type
The report that monomer is used as graphene oxide crosslinking agent.Modified three-dimensional graphene oxide space structure is stable, solves
The problem of easily being collapsed in water after traditional graphene oxide freeze-drying.
2nd, graphene oxide solution is first freeze-dried by the present invention using graphene oxide as pioneer, allows it to keep three
Fluff structure is tieed up, then crosslinking agent is chosen and fluorochemical monomer is modified.Modified graphene oxide foam three dimensions knot
Structure is more stablized, and with hydrophobic property, the adsorption effect of dyestuff is also changed.
3rd, method of modifying of the present invention is simple, it is not necessary to additionally increase preparation technology.Proposition of the invention innovative is using containing
The method that fluorine monomer is modified to graphene oxide, the report being modified currently without fluorochemical monomer to graphene oxide.This hair
Bright obtained modified graphene oxide foam bulk multi-hole, specific surface area is big, and density is low and Stability Analysis of Structures, preparation process letter
It is single, it is easy to control.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the modified graphene oxide prepared in the present invention.
Fig. 2 is the Fourier transform infrared figure of the modified graphene oxide prepared in the present invention.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
1) preparation of graphene oxide
By 1g native graphites and 1g sodium nitrate be added to 23mL98% from sulfuric acid, ice bath is stirred continuously, temperature control
At 3~5 DEG C, 4g liquor potassic permanganates, 30~40min of ice bath are successively added.Experimental provision is then transferred to oil bath pan
In, heat up 35~36 DEG C, middle temperature keeps 2h.Middle temperature adds water after terminating rises to 98 DEG C of high temperature, and high temperature keeps 30~40min, with this
7~the 10mL of hydrogen peroxide added water with 30%, obtains graphene oxide water solution.
2) separating-purifying
By obtained graphene oxide water solution in the case where rotating speed is 8000~12000r/min, 15~25min is rotated.Separation
Go out solid precipitation, plus the operation of deionized water repeated centrifugation.After centrifugation 5~7 times, it is with molecular cut off by gained suspension
8000 bag filter is dialysed, and dialysis to pH of suspension is centrifuged, sub-argument goes out suspension again close to neutrality.
3) preparation of modified graphene oxide
The crosslinking agent methylol propylene that quality is graphene oxide quality 5% is put into above-mentioned graphene oxide suspension
Acid amides, 50 DEG C of oil bath~60 DEG C, 2h；Again inwards add equivalent fluorochemical monomer hexafluoroisopropanol solution, 80 DEG C~85 DEG C of oil bath,
2h.4) freeze-drying of modified graphene oxide
By graphene oxide foam ultrasonic disperse 30min~50min after modification, after ultrasound, solution is poured into fixation
In mould, cryogenic freezing 24h is put into drying box into ice cube and dries 48h, prepare modified graphene oxide foam.
5) methylene blue solution is adsorbed
Configuration concentration is 0.05g/L methylene blue solution, is removed from the molds the modified graphene oxide bubble prepared
Foam, weighs and determines after quality, be put into methylene blue solution, and vibration absorption, each 10~20min determines its absorbance, it is known that
Untill absorbance is stable.Calculate adsorbance of the modified graphene oxide foam to methylene blue solution.
Claims (6)
1. a kind of hydrophobic adsorbent based on graphene oxide, it is characterised in that the preparation method of the adsorbent is as follows：
1) preparation method of graphene oxide：Take raw material native graphite, sodium nitrate, potassium permanganate and the concentrated sulfuric acid are respectively in ice bath
3 DEG C -8 DEG C complete oxidation experiment with stirring in 35 DEG C -98 DEG C of oil bath；
2) separating-purifying：By above-mentioned mixed liquor by centrifuge, dialysed afterwards with bag filter to the close neutrality of pH value of solution；
3) preparation of modified graphene oxide：Crosslinking agent function amide-type monomer and fluorochemical monomer are added into above-mentioned mixed liquor,
In 50-80 DEG C of oil bath reaction 2-8h；
4) freeze-drying of modified graphene oxide：By step 3) mixed liquor ultrasound after 30-60 minutes, be fixed in mould,
It is put into freeze drying box and is freeze-dried, prepares the modified graphene oxide foam i.e. present invention based on graphene oxide
Hydrophobic adsorbent.
2. the hydrophobic adsorbent according to claim 1 based on graphene oxide, it is characterised in that step 1) in it is natural
The mass ratio of graphite and potassium permanganate is controlled 1:3~1:6.
3. the hydrophobic adsorbent according to claim 1 based on graphene oxide, it is characterised in that step 2) in use
Bag filter scale be MD34 (8000-14000).
4. the hydrophobic adsorbent according to claim 1 based on graphene oxide, it is characterised in that step 3) described in
Crosslinking agent is NMA, and fluorochemical monomer is hexafluoroisopropanol.
5. the hydrophobic adsorbent according to claim 1 based on graphene oxide, it is characterised in that step 3) middle crosslinking
Agent consumption is the 2%~6% of graphene oxide quality, preferably 3%~5%；The consumption of fluorochemical monomer and the matter of graphene oxide
Amount is equivalent.
6. the hydrophobic adsorbent according to claim 1 based on graphene oxide, it is characterised in that step 4) when drying
Between be 48h~72h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710224088.9A CN107051404A (en) | 2017-04-07 | 2017-04-07 | A kind of hydrophobic adsorbent based on graphene oxide |
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| CN201710224088.9A CN107051404A (en) | 2017-04-07 | 2017-04-07 | A kind of hydrophobic adsorbent based on graphene oxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108030704A (en) * | 2017-12-21 | 2018-05-15 | 北京工商大学 | Botanical hair dye and preparation method using graphene oxide as dyeing auxiliaries |
| CN113274989A (en) * | 2021-05-31 | 2021-08-20 | 南京信息工程大学 | Preparation method of polyurethane foam-based hydrophobic adsorption material |
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| CN102910625A (en) * | 2012-11-14 | 2013-02-06 | 北京理工大学 | Graphene oxide aerogel, preparation method and application |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
| CN104743550A (en) * | 2015-03-24 | 2015-07-01 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional macroscale graphene and preparation method thereof |
| CN105295265A (en) * | 2015-12-07 | 2016-02-03 | 郑州轻工业学院 | Modified polyvinylidene fluoride super-hydrophobic material and preparation method thereof |
| CN105731432A (en) * | 2016-01-18 | 2016-07-06 | 杭州师范大学 | Preparation method of silane functionalized graphene aerogel material |
| CN106517171A (en) * | 2015-09-10 | 2017-03-22 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene aerogel |
-
2017
- 2017-04-07 CN CN201710224088.9A patent/CN107051404A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910625A (en) * | 2012-11-14 | 2013-02-06 | 北京理工大学 | Graphene oxide aerogel, preparation method and application |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
| CN104743550A (en) * | 2015-03-24 | 2015-07-01 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional macroscale graphene and preparation method thereof |
| CN106517171A (en) * | 2015-09-10 | 2017-03-22 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene aerogel |
| CN105295265A (en) * | 2015-12-07 | 2016-02-03 | 郑州轻工业学院 | Modified polyvinylidene fluoride super-hydrophobic material and preparation method thereof |
| CN105731432A (en) * | 2016-01-18 | 2016-07-06 | 杭州师范大学 | Preparation method of silane functionalized graphene aerogel material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108030704A (en) * | 2017-12-21 | 2018-05-15 | 北京工商大学 | Botanical hair dye and preparation method using graphene oxide as dyeing auxiliaries |
| CN113274989A (en) * | 2021-05-31 | 2021-08-20 | 南京信息工程大学 | Preparation method of polyurethane foam-based hydrophobic adsorption material |
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Application publication date: 20170818 |