CN106693898A - Porous reduced graphene oxide oil absorption material with controllable doping level and preparation method thereof - Google Patents
Porous reduced graphene oxide oil absorption material with controllable doping level and preparation method thereof Download PDFInfo
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- CN106693898A CN106693898A CN201611018003.3A CN201611018003A CN106693898A CN 106693898 A CN106693898 A CN 106693898A CN 201611018003 A CN201611018003 A CN 201611018003A CN 106693898 A CN106693898 A CN 106693898A
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- oil absorption
- graphene oxide
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- 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
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Abstract
The invention discloses a porous reduced graphene oxide oil absorption material with a controllable doping level and a preparation method thereof. The porous reduced graphene oxide oil absorption material with the controllable doping level is of a hierarchical porous structure stacked layer by layer; a reduced graphene oxide aerogel is adopted as a substrate; and amino acid is doped in a framework of the reduced graphene oxide aerogel. The preparation method provided by the invention comprises the steps of firstly mixing graphene oxide and an amino acid reducing agent dissolving solution; then obtaining a reduced graphene oxide hydrogel through a high pressure hydrothermal method; and finally, washing the hydrogel, freezing at low temperature for pore-forming, and obtaining the porous reduced graphene oxide oil absorption material. The oil absorption material provided by the invention has favorable hydrophobicity, has a better adsorption capacity on an oil product and an organic pollutant, and achieves the aim of oil-water separation in an oil-water composite environment; and meanwhile, pore diameter distribution and a pore structure of the material can be regulated and controlled through the control on the doping level, the selective oil absorption of the material is promoted, and the selective adsorption of the oil product is realized.
Description
Technical field
The invention belongs to technical field of nano material, specifically, it is related to the porous reduction-oxidation that a kind of doping level is controllable
Graphene oil absorption material and preparation method thereof.
Background technology
Graphene aerogel have specific surface area higher and multi-stage artery structure characteristic, ultracapacitor, lithium battery,
Catalysis, adsorbing domain have relatively broad application.Oil absorption material absorption to the treatment of marine oil spill and organic pollution very
Effectively, the features such as easily being reclaimed due to its efficient, economy, oil product and organic matter, is widely used in marine oil spill contamination accident
Emergency processing.But traditional oil absorption material is due to its poor hydrophobicity, relatively low oil absorbency, potential bio-toxicity with
And the features such as reclaiming is difficult to, the drawbacks of have of all kinds in actual applications, thus need badly and find new oil absorption material and come
Make up these materials defect in the application.
The elementary cell of π-π structures imparts the good hydrophobicity of grapheme material, block Graphene oil absorption material, tool
There is original oil absorbency and relatively low density, circulate high with recovery utilization rate.But traditional graphene aerogel oil absorption material
Although the adsorption capacity with oil product and organic pollution, due to the uneven of its aperture, poor repeatability thus to oil product
Selectivity is poor.Amino acids chemicals rarely has people to report the reduction assembling process of graphene oxide, while under normal circumstances
The doping level of prepared redox graphene aeroge is uncontrollable.And the doping level of chemical reducing agent can be to material
The oil absorbency of material, mechanical property produce influence, therefore how to obtain the controllable redox graphene aeroge of doping level,
The selective oil suction that graphite oxide aerogel can preferably be completed is still a huge challenge.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of controllable porous reduction-oxidation of doping level
Graphene oil absorption material and preparation method thereof.Preparation method doping level in the present invention is controllable, the porous oxygen reduction fossil for obtaining
Black alkene oil absorption material can realize the selective absorption to oil product and organic contamination.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of doping level controllable porous redox graphene oil absorption material, and it is many of stacked in multi-layers
Level pore structure；It is doped with ammonia with redox graphene aeroge as substrate in the skeleton of redox graphene aeroge
Base acid.Preferably, the amino acid is selected from one or more in phenylalanine, tyrosine or glycine.Porous aperture is in 1-
Between 20 μm.
The present invention also provides a kind of preparation method of the controllable porous redox graphene oil absorption material of above-mentioned doping level,
Comprise the following steps that：
(1) graphene oxide aqueous dispersions are prepared, reducing agent and graphene oxide aqueous dispersions is mixed；Wherein：It is described
Reducing agent is amino acid；
(2) mixed liquor and reducing agent the lysate mixing for obtaining step (1)；Wherein：Reducing agent lysate is acid molten
Liquid or alkaline solution；Acidic materials in the acid solution be selected from formic acid, acetic acid or ethanedioic acid any one and it is several
Kind；Alkaline matter in alkaline solution be selected from ammoniacal liquor, NaOH or sodium acid carbonate any one and it is several；
(3) mixed liquor that step (2) is obtained is carried out into hydro-thermal reaction, obtains redox graphene hydrogel；
(4) after redox graphene hydrogel is washed, freeze-drying under vacuum obtains amino acid doping
Porous graphene airsetting oil absorption material.
In the present invention, in step (1), the amino acid is selected from the one kind or several in phenylalanine, tyrosine or glycine
Kind.
In the present invention, the mass ratio of reducing agent and graphene oxide is 1：2~5：1.
In the present invention, in step (3), between 90~180 DEG C, the reaction time is 8-48h to the temperature of hydro-thermal reaction.
In the present invention, in step (4), with ethanol and water washing redox graphene hydrogel；Before freeze-drying, by also
Former graphene oxide hydrogel soaks in concentration is for the weak aqua ammonia of 1wt%~5wt%.
In the present invention, in step (4), the temperature of freeze-drying is -48 DEG C to -60 DEG C.
Compared to the prior art, the beneficial effects of the present invention are：
(1) a kind of controllable porous redox graphene oil absorption material of doping level proposed by the present invention, is a kind of amino
As reducing agent, redox graphene aeroge for substrate and with good oil absorbency, regulatable feature is received for acid
Rice material.Due to introducing reducing agent lysate in preparation process, (cosolvent is controlled with pH value, by with good hydrotropy
Acidity or alkaline medium and reducing agent be formulated according to a certain percentage), in different pH conditions and different cosolvents
Under effect, the reduction of reducing agent is promoted or is suppressed, so as to further cause the doping of reducing agent to be controlled
System, thus can be good control prepared by redox graphene aeroge doping level, the control of doping level can be right
The pore-size distribution and pore structure of material are regulated and controled, so as to promote the selective oil suction of material, realize the selection absorption of oil product；
(2) due to the amino acids reducing agent nonhazardous effect for introducing, after material is prepared completely, without further drop
Low bio-toxicity can be used in input water body；
(3) there is the hydrophobic surface of more π-pi-conjugated formation on the surface of redox graphene aeroge oil absorption material, together
When graphene oxide reduction induction occur assembling process in can produce substantial amounts of pore structure, these pore structures be oil product
Substantial amounts of space is provided with the absorption of graphene oxide, therefore there is preferable adsorption capacity to oil product and organic pollution；
(4) the redox graphene aeroge oil absorption material for obtaining has relatively low density, hydrophobicity higher；
(5) reaction condition green non-pollution, prepares simple, easily repetition.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the oil absorption material in the embodiment of the present invention 1.
Fig. 2 is the Raman scanning figure of the oil absorption material in the embodiment of the present invention.
Fig. 3 is oil absorption material in the embodiment of the present invention to different oil products and the adsorption capacity schematic diagram of organic pollution.
Specific embodiment
Below by embodiment, the present invention is further illustrated, and its purpose is only that and is best understood from present disclosure
The protection domain being not intended to limit the present invention：
Embodiment 1~6
(1) 750mg graphene oxide solids are weighed in beaker, 100ml deionized waters are added, is configured to 7.5mg/ml's
Graphene oxide dispersion, ultrasonic disperse is uniform；
(2) from step 1) 10ml is measured in the dispersion liquid that obtains is transferred in 30ml straight tube reaction bulbs；
(3) weigh the tyrosine reducing agent of 75mg, add step 2) in the dispersion liquid that obtains；
(4) in step 3) obtained by solution in add with formic acid as cosolvent and be formulated by acid medium of formic acid
PH be 2 aqueous formic acid, and load height to 80%, fully vibration after ultrasonic disperse it is uniform；
(5) by step 4) obtained by reaction bulb be put into the autoclave with polytetrafluoro liner, at a temperature of 120 DEG C
Reacted, reacted 32 hours；
(6) after question response liquid natural cooling, gained gel is washed with deionized, ethanol washing, weak aqua ammonia immersion, so
The freeze-drying under -55 DEG C of vacuum conditions again afterwards, obtains the porous graphene airsetting oil absorption material of amino acid doping.
Made above obtain is tyrosine redox graphene aeroge under formic acid (2) environment, is designated as embodiment 1.
Fig. 1 is ESEM (FE-SEM, S-4800, Hitachi, Japan) image of the oil absorption material in the embodiment of the present invention 1, is said
The redox graphene of bright preparation has compared with horn of plenty and unordered pore passage structure, aperture about 2um to 10um.
Embodiment 2-6 experimental procedures are same as Example 1, the difference of the reducing agent cosolvent of preparation, specific as follows：
| Embodiment | pH | Acid-base property controls medium |
| Embodiment 1 | 2 | Formic acid |
| Embodiment 2 | 4 | Formic acid |
| Embodiment 3 | 6 | Formic acid |
| Embodiment 4 | 8 | One hydration ammonia |
| Embodiment 5 | 10 | One hydration ammonia |
| Embodiment 6 | 12 | One hydration ammonia |
The redox graphene aeroge of amino acid doping is prepared according to above-described embodiment, by cosolvent and dispersion liquid
The synergy of pH, it is possible to achieve the control that redox graphene aeroge adulterates to reducing agent, so as to further regulate and control
Oil absorbency；More relatively low doping level, and a best oil absorbency are shown as pH=2.
Fig. 2 is the Raman scanning figure of the oil absorption material in embodiment of the present invention 1- embodiments 6, as a result represents that the present invention is implemented
The Raman scanning figure of the oil absorption material in example；Result shown in the case of different soda acids, the amino acid of the oil absorption material for obtaining
Doping level is different.Specifically, in the presence of with ammoniacal liquor as alkalescence control thing, the doping level of material is with the increase (ammonia of alkalescence
The shared proportion increase in reduction of gas) and reduce；In the presence of with formic acid as acidity control thing, the doping level body of material
An existing no regularity, and with maximum doping level when pH is 4.
Fig. 3 is that the oil absorption material in embodiment of the present invention 1-6 is illustrated to the adsorption capacity of different oil products and organic pollution
Figure.Show the selective adsorption capacity of material.
Specific oil suction method is as follows：
1. the quality that assay balance weighs fully dried aeroge sample is Wa；
2. the aeroge sample after the completion of 1) middle weighing is completely submerged in adsorbate (pure organic pollution or oil product)
In, stand 30min and ensure that aeroge completes sufficiently absorption；
3. the Graphene gel in 2) fully after absorption is taken out, the adsorbate of remained on surface is dried with qualitative filter paper；
4. aeroge in 3) is placed on assay balance and weighed, obtain quality for Wb
The adsorbance computing formula Q=(W of materialb–Wa)/WaUnit g g-1。
Result shows that, when reducing agent lysate concentration control ph is 2, the oil absorption material for obtaining is to dichloromethane and stone
Oily ether adsorption capacity shows most strong compared with other pH controls；When reducing agent lysate concentration control ph is 2, the suction for obtaining
Light wood material shows highest to dichloromethane and petroleum ether adsorption capacity compared with other pH controls；When reducing agent lysate concentration control
When pH processed is 4, the oil absorption material for obtaining is higher to the adsorption capacity of dichloromethane, but minimum to the adsorption capacity of petroleum ether, because
And show good oil suction selectivity.
The above is only the basic explanation under present inventive concept, and according to technical scheme done it is any etc.
Effect conversion, all should belong to protection scope of the present invention.
Claims (9)
1. the controllable porous redox graphene oil absorption material of a kind of doping level, it is characterised in that：It is many of stacked in multi-layers
Level pore structure；It is doped with ammonia with redox graphene aeroge as substrate in the skeleton of redox graphene aeroge
Base acid.
2. the controllable porous redox graphene oil absorption material of doping level according to claim, it is characterised in that：Institute
Amino acid is stated selected from one or more in phenylalanine, tyrosine or glycine.
3. the controllable porous redox graphene oil absorption material of doping level according to claim 1, it is characterised in that：It is many
Hole aperture is between 1-20 μm.
4. the system of the controllable porous redox graphene oil absorption material of a kind of doping level according to one of claim 1-3
Preparation Method, it is characterised in that comprise the following steps that：
(1) graphene oxide aqueous dispersions are prepared, reducing agent and graphene oxide aqueous dispersions is mixed；Wherein：The reduction
Agent is amino acid；
(2) mixed liquor and reducing agent the lysate mixing for obtaining step (1)；Wherein：Reducing agent lysate be acid solution or
Person's alkaline solution；Acidic materials in the acid solution be selected from formic acid, acetic acid or ethanedioic acid any one and it is several；Alkali
Property solution in alkaline matter be selected from ammoniacal liquor, NaOH or sodium acid carbonate in any one and it is several；
(3) mixed liquor that step (2) is obtained is carried out into hydro-thermal reaction, obtains redox graphene hydrogel；
(4) after redox graphene hydrogel is washed, freeze-drying under vacuum obtains the porous of amino acid doping
Graphene airsetting oil absorption material.
5. preparation method according to claim 4, it is characterised in that in step (1), the amino acid is selected from phenylpropyl alcohol ammonia
One or more in acid, tyrosine or glycine.
6. preparation method according to claim 4, it is characterised in that the mass ratio of reducing agent and graphene oxide is 1：2
~5：1.
7. preparation method according to claim 4, it is characterised in that in step (3), the temperature of hydro-thermal reaction 90~
Between 180 DEG C, the reaction time is 8-48h.
8. preparation method according to claim 4, it is characterised in that in step (4), with ethanol and water washing reduction-oxidation
Graphene hydrogel；Before freeze-drying, by redox graphene hydrogel in concentration in the weak aqua ammonia of 1wt%~5wt%
Immersion.
9. preparation method according to claim 4, it is characterised in that in step (4), the temperature of freeze-drying is -48 DEG C
To -60 DEG C.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107331530A (en) * | 2017-06-26 | 2017-11-07 | 中国科学技术大学 | A kind of low-temperature-doped graphene and preparation method thereof and ultracapacitor |
| CN107539980A (en) * | 2017-09-07 | 2018-01-05 | 马鞍山中粮生物化学有限公司 | A kind of novel graphite alkene aerogel material and preparation method thereof |
| CN107792901A (en) * | 2017-12-05 | 2018-03-13 | 苏州贝多环保技术有限公司 | A kind of novel oil absorption cotton |
| CN108212083A (en) * | 2017-12-28 | 2018-06-29 | 西南石油大学 | A kind of oil suction carbon sponge and preparation method thereof |
| CN108461309A (en) * | 2018-04-25 | 2018-08-28 | 山西大学 | A kind of preparation method of graphene film electrode material |
| CN110155993A (en) * | 2019-06-27 | 2019-08-23 | 中素新科技有限公司 | Hydrophobic graphene aerogel and its preparation method and application |
| CN110156432A (en) * | 2019-06-27 | 2019-08-23 | 中素新科技有限公司 | Carbon fiber composite graphite alkene aeroge and its preparation method and application |
| CN110327851A (en) * | 2019-06-27 | 2019-10-15 | 中素新科技有限公司 | Elastic graphite alkene aeroge and its preparation method and application |
| CN112079349A (en) * | 2020-08-25 | 2020-12-15 | 中国科学院兰州化学物理研究所 | Method for preparing nitrogen-doped porous graphene nano material through limited-area combustion and application |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107331530A (en) * | 2017-06-26 | 2017-11-07 | 中国科学技术大学 | A kind of low-temperature-doped graphene and preparation method thereof and ultracapacitor |
| CN107539980A (en) * | 2017-09-07 | 2018-01-05 | 马鞍山中粮生物化学有限公司 | A kind of novel graphite alkene aerogel material and preparation method thereof |
| CN107792901A (en) * | 2017-12-05 | 2018-03-13 | 苏州贝多环保技术有限公司 | A kind of novel oil absorption cotton |
| CN108212083A (en) * | 2017-12-28 | 2018-06-29 | 西南石油大学 | A kind of oil suction carbon sponge and preparation method thereof |
| CN108461309A (en) * | 2018-04-25 | 2018-08-28 | 山西大学 | A kind of preparation method of graphene film electrode material |
| CN110155993A (en) * | 2019-06-27 | 2019-08-23 | 中素新科技有限公司 | Hydrophobic graphene aerogel and its preparation method and application |
| CN110156432A (en) * | 2019-06-27 | 2019-08-23 | 中素新科技有限公司 | Carbon fiber composite graphite alkene aeroge and its preparation method and application |
| CN110327851A (en) * | 2019-06-27 | 2019-10-15 | 中素新科技有限公司 | Elastic graphite alkene aeroge and its preparation method and application |
| CN110155993B (en) * | 2019-06-27 | 2021-01-26 | 中素新科技有限公司 | Hydrophobic graphene aerogel and preparation method and application thereof |
| CN110327851B (en) * | 2019-06-27 | 2021-07-27 | 中素新科技有限公司 | Elastic graphene aerogel and preparation method and application thereof |
| CN110156432B (en) * | 2019-06-27 | 2021-11-26 | 中素新科技有限公司 | Carbon fiber composite graphene aerogel and preparation method and application thereof |
| CN112079349A (en) * | 2020-08-25 | 2020-12-15 | 中国科学院兰州化学物理研究所 | Method for preparing nitrogen-doped porous graphene nano material through limited-area combustion and application |
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