CN110496609A - A kind of graphene oxide/hydroxyapatite nano line multi-function absorption aeroge and preparation method thereof - Google Patents
A kind of graphene oxide/hydroxyapatite nano line multi-function absorption aeroge and preparation method thereof Download PDFInfo
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- CN110496609A CN110496609A CN201910909091.3A CN201910909091A CN110496609A CN 110496609 A CN110496609 A CN 110496609A CN 201910909091 A CN201910909091 A CN 201910909091A CN 110496609 A CN110496609 A CN 110496609A
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- aeroge
- graphene oxide
- nano line
- hydroxyapatite nano
- hydroxyapatite
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Classifications
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
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- B01J20/28014—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 form
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention relates to a kind of graphene oxide/hydroxyapatite nano line multi-functions to adsorb aeroge, is able to achieve the efficient absorption of fluorine ion in various oils/organic solvents and water.Its prepare the following steps are included: (1) by GO aqueous dispersions, HAP nano wire aqueous dispersions and chemical reducing agent mix, and stir, ultrasound makes it be uniformly dispersed；(2) the slight electronation-freezing thawing-drastic reduction process self assembly of dispersion liquid progress will be blended and obtain rGO/HAP hydrogel；(3) above-mentioned hydrogel progress freeze-dried is obtained into rGO/HAP aeroge；(4) high temperature cabonization processing or surface hydrophilic modification are carried out to realize the efficient absorption of different organic solvents or fluorine ion to above-mentioned aeroge.Its method is simple, quick, and reaction condition is mild, has excellent physical and chemical performance and mechanical property, adsorption capacity is high, the high fluorine ion waste water of efficient process and insoluble oil or organic solvent waste water can be contained, and can repeatedly used, there is good actual application prospect.
Description
Technical field
The present invention relates to adsorbent material field, in particular to a kind of graphene oxide/hydroxyapatite nano line multi-function
Adsorb aeroge.
Background technique
In recent years, as economic fast development and the size of population increase sharply, water pollution problems becomes increasingly serious, to aquatic
The health of biology and human body causes to seriously endanger, it has also become influences the larger threat of human survival and sustainable development.In addition, water
The type of body pollution object is also more and more extensive, and ingredient becomes increasingly complex, in addition to the most common oils (such as crude oil) or organic molten
Except agent pollutant, a large amount of pollutants (such as fluorine ion, heavy metal, pesticide, dyestuff) difficult to degrade are emitted into water body, right
Earth's surface and underground water cause serious persistent pollution.Removing numerous pollutants in water body how scientific and efficiently, oneself passes through
One of hot spot as domestic and international academic and engineering circles research.
The method of removal water pollutant mainly has absorption, filtering, biodegrade and light degradation etc., and wherein absorption method has
Efficiently, environmental protection, it is at low cost the advantages that and become administer water pollution prefered method.Traditional adsorbent material for example active carbon, clay,
Equal adsorption efficiencies and ability are lower and easily cause secondary pollution, so being badly in need of a kind of having high absorption capacity, highly selective, excellent
The novel absorption material of recycling.More three-dimensional (3D) porous material such as polymer matrix foam, sponge etc. is reported at present
Although the absorption of the organic solvents such as oils may be implemented, but exists and have a single function, adsorption capacity and the low disadvantage of selectivity.
(Ge, J., et al. .ACS Appl Mater Interfaces, 2018.10 (46): p.40274-40285.) are adopted Ge et al.
With 46~96 times that the adsorbance that melamine sponge is used for organic solvent in oil water mixture is only own wt.Compared to it
Under, graphene-based aeroge has excellent hydrophobic/lipophilicity, low-density, high-ratio surface as a kind of emerging 3D porous material
The special performances such as long-pending, good chemical stabilization and thermal stability, have broad application prospects in advanced adsorbing domain.Bi et al.
((Bi, H., et al. .Advanced Functional Materials, 2012.22:p.4421-4425.) is using oxidation stone
Black alkene is raw material, obtains graphene hydrogel using hydrothermal reduction method, then it is carried out being freeze-dried graphene-based sponge can
To realize the absorption to a variety of organic solvents such as toluene, chloroform, but it is only 20~86 times of own wt that adsorption rate is lower, in addition
Realize that recycling for material has that energy consumption is big and easily causes secondary pollution by burning facture.This is primarily due to
Pure graphene aerogel mechanical property is poor, limits the way of recycling of graphene-based gel rubber material adsorbate.It is noticeable
It is that monodimension nanometer material (such as carbon nanotube, nanofiber), polymer (polyvinyl alcohol, polyvinylpyrrolidone etc.) is added
Or chemical cross-linking agent (glutaraldehyde etc.) etc. can effectively improve the mechanical strength and compression resilience of graphene-based aeroge, into
And the effective desorption and circulation absorption performance of gel rubber material are realized by simple physical impact mode.For example, Zhan et al.
(2017.10 (1): p.1093-1103.) Zhan, W., et al. .ACS Applied Materials&Interfaces will
The multi-walled carbon nanotube (MWCNT-PDA) of one-dimensional PDA functionalization is introduced into graphene aerogel network, has been synthesized a kind of strong
Graphene/carbon nano-tube composite aerogel, and can be recycled 10 times by way of simple " absorption-extruding ".Xiao etc.
People (Xiao, J., et al. .Carbon, 2017.123:p.354-363.) has synthesized a kind of go back using hydro-thermal local reduction way
Former graphene oxide/polyvinyl alcohol aeroge, the aeroge after hydrophobically modified can adsorb common grease on the water surface and
Organic solvent, adsorption rate can achieve 67~155 times of own wt.Nevertheless, these above-mentioned graphene-based aeroges exist
There are still the following problems in terms of preparation and adsorption applications: (1) one-dimensional carbon nanotube preparation process is complex and costly；(2)
Hydro-thermal method need high temperature and pressure condition and special reaction unit, increase the difficulty of practical application；It is (3) functional single,
General graphene aerogel can only realize the absorption of part organic solvent or oils, it is difficult to realize the processing of Complex water body pollutant
(such as fluorine ion).
It is worth noting that, hydroxyapatite (HAP) is the main constituents of human body and animal skeleton, belong to hexagonal crystal
System, with special crystal structure, surface nature and superior bio compatibility, therefore often by as a kind of nothing haveing excellent performance
Machine ion and organic matter absorption and exchange material, with fields such as improvement for wastewater treatment, contaminated soil.Such as patent
CN104289181A discloses a kind of magnetic hydroxylapatite graphene oxide adsorbent, in graphene oxide system Central Plains
Position growth magnetic hydroxylapatite obtains magnetic hydroxylapatite/graphene oxide powder, and for adsorbing the heavy metal in water
Ion.Although the patent is prepared for magnetic hydroxylapatite graphene oxide adsorbent, but it has following obvious problem:
(a) common hydroxyapatite is used, specific surface area is smaller；(b) composite material obtained be powder morphology, not formed three
Structure is tieed up, porosity is lower；(c) material after adsorbing is difficult to recycle, and cannot achieve recycling.
In view of the above problems, we will have good biocompatibility, excellent heat and chemical stability, Gao Rou in the present invention
Toughness, low cost and one-dimensional hydroxyapatite (HAP) nano wire with exhibiting high surface activated adoption site are as graphene-based
The efficient second collaboration component of aeroge network.The introducing of HAP assigns the graphene-based several significant advantages of aeroge: (a) closing
At overlength hydroxyapatite nano line acted on and can be achieved to graphene airsetting using its strong hydrogen bonding between graphene oxide
2D graphene sheet layer is effectively adhered and humidification in glue, therefore can significantly improve the mechanical property of graphene-based aeroge.
(b) hexagonal crystallographic texture of HAP makes it have very strong ion-exchange capacity, and nanoscale apatite has bigger specific surface
The advantages that product, high activity, therefore it can assign graphene-based aeroge good fluorine ion adsorption capacity, realize that its is excellent more
Function characterization of adsorption.(c) preparation of hydroxyapatite nano line enhances component (such as carbon nanotube) original compared to traditional one-dimensional
Material is easy to get, preparation process is simple, at low cost, so that the composite aerogel shows good actual application prospect.It may be noted that
, enhance the mechanical property of graphite oxide aerogel using hydroxyapatite nano line and assign its multi-functional characterization of adsorption
Research have not been reported so far.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, it is an object of that present invention to provide a kind of graphene oxide/hydroxyapatites to receive
Multi-functional absorption aeroge of rice noodles and preparation method thereof solves graphene-based aeroge preparation cost height, needs in the prior art
Complex reaction device；The poor mechanical property of pure graphene-based aeroge, influences material circulation service efficiency；Two-dimentional membrane material or
Dusty material adsorption capacity and selectivity are low；The thorny problems such as graphene-based aeroge adsorption function is single.
The present invention is about a kind of graphene oxide/hydroxyapatite nano line multi-function absorption aeroge and its preparation side
Method, prepares that cost of material is low, and step is simple, time-consuming shorter；Enhanced using the overlength hydroxyapatite nano line of high-flexibility
The mechanical property of graphene-based aeroge；Excellent wetting selection performance makes it have high adsorptive selectivity；Hydroxyapatite
Introducing the graphene-based aeroge of imparting also has high absorption capacity for fluorine ion etc. in addition to adsorbing oily phase function, so that oxidation stone
Black alkene/hydroxyapatite nano line aeroge shows multi-functional adsorption property.
Technical scheme is as follows:
A kind of graphene oxide/hydroxyapatite nano line multi-function absorption aeroge preparation method, wherein including with
Lower step:
1) GO aqueous dispersions, HAP nano wire aqueous dispersions and chemical reducing agent are mixed in a certain ratio, and stir, surpasses
Sound makes it be uniformly dispersed；
2) blending dispersion liquid is slightly restored-is freezed thawing-drastic reduction process self assembly and obtain rGO/HAP water-setting
Glue；
3) above-mentioned hydrogel is successively carried out to freeze-dried and obtains rGO/HAP aeroge；
4) high temperature cabonization processing or surface hydrophilic modification are carried out to above-mentioned aeroge.
Further, the diameter of the hydroxyapatite nano line is between 10~500nm, length 1~100 μm it
Between, the thickness of graphene oxide is in 1~10nm, and lamella size is between 1~10 μm, hydroxyapatite nano line/graphite oxide
Make the mixing suspension liquid of aqueous phase of the two that there is good dispersibility by hydrogen bond action between alkene.
The graphene oxide/hydroxyapatite nano line multi-function absorption aeroge preparation method, wherein described
Graphene oxide in step 1) is prepared using Hummers method, and the concentration of graphene oxide aqueous dispersions is 1~20mg/mL；Hydroxyl
Base apatite nano wire is 1 using calcium oleate presoma-solvent-thermal method preparation, the concentration of hydroxyapatite nano line aqueous dispersions
~15mg/mL；The mass ratio of hydroxyapatite and graphene oxide is 1/15~5；Chemical reducing agent be vitamin C, hydrogen iodide,
Tannic acid, citric acid, ethylenediamine, dopamine, sodium ascorbate, hydrazine hydrate, ammonium hydroxide, thiocarbamide, glucose, chitosan, cyclodextrin,
One of sodium hydrogensulfite, vulcanized sodium, hydroquinone or a variety of mixtures, the mass ratio of chemical reducing agent and graphene oxide
It is 1/15~10；Carrying out magnetic agitation condition to mixed dispersion liquid is 150~1500rpm/30~180min；Ultrasonic treatment condition
For 200~750W/25~500kHz/1~120min.
The graphene oxide/hydroxyapatite nano line multi-function absorption aeroge preparation method, wherein described
Step 2) mild or moderate reducing condition is 50~90 DEG C/20min~48h；Freezing conditions are -5 DEG C~-196 DEG C/5min~48h: deep
Degree reducing condition is 50~90 DEG C/20min~48h.
The graphene oxide/hydroxyapatite nano line multi-function absorption aeroge preparation method, wherein described
Step 3) carries out vacuum refrigeration-drying condition are as follows: temperature -30~-55 DEG C, vacuum degree are 5.0~55Pa, and the time is 6~72h.
The graphene oxide/hydroxyapatite nano line multi-function absorption aeroge preparation method, wherein described
Step 4) carries out high temperature cabonization condition are as follows: maximum temperature is 400~1000 DEG C, and heating rate is 5~20 DEG C/min, constant temperature time
For 30~180min, required inert atmosphere is one of nitrogen, argon gas, helium, neon.Former silicon can be selected in hydrophilic modifying component
Sour tetra-ethyl ester, chitosan, dopamine, tannic acid, polyethyleneimine etc. are or mixtures thereof one such；The mode of hydrophilic modifying
Dip-coating, spraying etc. can be used；Hydrophilic modifying solution concentration be 0.2~40mg/mL, volume 0.1-50mL, modification time be 2~
24h。
A kind of graphene oxide/hydroxyapatite nano line multi-function absorption aeroge, the gas handled by high temperature cabonization
Gel can be used in the absorption of organic solvent or insoluble oil in water；It can be used by the aeroge that surface hydrophilic modification is handled
The absorption of Yu Shuizhong fluorine ion.
The invention has the following advantages: 1) graphene oxide/hydroxyapatite nano line multi-function prepared by is inhaled
Attached aeroge prepares that raw material is easy to get, step is simple, at low cost；2) the oxidation stone compared to pure graphene aerogel, in the present invention
Black alkene/hydroxyapatite nano line Mechanical Properties of Aerogels is preferable, and then makes it have good compression recovery performance；3) it compares
The oil removing material in traditional water, the graphene-based aeroge in the present invention have super wetting selectivity, may be implemented to have in water
The selective absorption of solvent；4) compared to two-dimentional membrane material or dusty material, three-dimensional aeroge of the invention has high ratio
Surface and porosity, adsorption capacity is high, can arrive the hundred times of own wt；5) compared to traditional adsorbent material by burning or
Recycling is realized in distillation, and graphene aerogel can realize the circulation of material by simple " extruding-absorption " in the present invention
It uses, even if still having good compression recovery performance after infiltrating organic solvent；6) graphene oxide/hydroxyl of the invention
Apatite nano wire aeroge can realize the multi-functional characterization of adsorption of insoluble oil/organic solvent and fluorine ion in water, have
Stronger versatility.
Detailed description of the invention
Fig. 1 is graphene oxide/hydroxyapatite nano line aeroge preparation route figure in embodiment 1.
Fig. 2 is graphene oxide/hydroxyapatite nano line aeroge digital photograph obtained in embodiment 1.
Fig. 3 is that water connects redox graphene/hydroxyapatite nano line aeroge in air after being carbonized in embodiment 1
Feeler test chart.
Fig. 4 is that oil connects redox graphene/hydroxyapatite nano line aeroge in air after being carbonized in embodiment 1
Feeler test chart.
Fig. 5 is that redox graphene/hydroxyapatite nano line aeroge compression rebound tests number after embodiment 1 is carbonized
Code photo.
Redox graphene/hydroxyapatite nano line aeroge is by the way that " absorption-is squeezed after Fig. 6 is carbonized for embodiment 1
Pressure " mode circulation absorption n-hexane.
Fig. 7 be embodiment 1 in after hydrophilic modifying redox graphene/hydroxyapatite nano line aeroge in air
Middle water contact angle test chart.
Specific embodiment
The present invention provides a kind of graphene oxide/hydroxyapatite nano line multi-function absorption aeroge and preparation method,
To make the purpose of the present invention, technical solution and effect clearer, clear and definite, the present invention is described in more detail below.It should
Understand, the specific embodiments described herein are merely illustrative of the present invention, is not intended to limit the present invention.
Embodiment 1: graphene oxide/hydroxyapatite nano line multi-function absorption aeroge preparation route such as Fig. 1, tool
Body is as follows, and (wherein graphene oxide concentration is 3mg/mL, hydroxyl to configuration 6mL hydroxyapatite nano line/graphene oxide dispersion
Base apatite nano wire concentration is 3mg/mL): it takes the graphene oxide (18mg/mL) of 1mL in beaker, the hydroxyl of 2mL is added
The sodium ascorbate (100mg/mL) of 0.9mL is added in apatite nano wire (9mg/mL), 2.1mL deionized water is added, to mixing
Liquid carries out ultrasonic disperse (300W/250kHz/5min) and magnetic agitation (600rpm/90min) processing, obtains evenly dispersed mix
Close dispersion liquid.Dispersion liquid is taken into flat bottle and carries out slight reduction assembling 2h under the conditions of 60 DEG C；Refrigerator is put into after cooling
(- 18 DEG C) freezing 12h of lower layer；10h is restored in 60 DEG C of oil bath pans again after thawing to obtain redox graphene/hydroxyapatite and receive
Rice noodles hydrogel；It is used deionized water dialysis 3 days；The hydrogel dialysed is put into (- 18 DEG C) freezing 15h of refrigerator freezing layer
Afterwards, at -48 DEG C, vacuum degree 10.0Pa is freeze-dried 48h, obtains redox graphene/hydroxyapatite nano line airsetting
Glue.
By it, carbonization treatment 1h (under nitrogen protection) obtains graphene-based aeroge at 800 DEG C.As shown in Fig. 2, the airsetting
The integrally formed property of glue is preferable；For the aeroge to the contact angle of water up to 148 ° (Fig. 3), oil droplet can enter gel with rapid osmotic simultaneously
(Fig. 4), therefore there is super-hydrophobic and super-oleophilic, therefore can realize oily waste water with the oil pollutant in high-selectivity adsorption water
The processing of water, for chloroform adsorbance up to 120 times of own wt, and there is high compression-resilience (Fig. 5), pass through
The desorption for adsorbing oily phase and circulation absorption ability can be thus achieved in simple squeeze (Fig. 6 is oily phase with n-hexane).
In addition the Dopamine hydrochloride buffering by redox graphene/hydroxyapatite nano line aeroge in 2mg/mL is molten
After impregnating 6h in liquid, dry 5h obtains the modified redox graphene/hydroxyl phosphorus in poly-dopamine surface in 50 DEG C of vacuum drying ovens
Lime stone nano wire aeroge shows Superhydrophilic (Fig. 7, water contact angle are 0 °), has high suction to the fluorine ion in water
Attached property, adsorption capacity may be up to 78mg/g.
Embodiment 2: (wherein graphene oxide concentration is configuration 6mL hydroxyapatite nano line/graphene oxide dispersion
5mg/mL, hydroxyapatite nano line concentration are 1mg/mL): it takes the graphene oxide (15mg/mL) of 2mL in beaker, is added
The sodium ascorbate (100mg/mL) of 0.3mL is added in the hydroxyapatite nano line (6mg/mL) of 1mL, and 2.7mL deionization is added
Water carries out ultrasonic disperse (300W/250kHz/8min) to mixed liquor and magnetic agitation (600rpm/60min) is handled, obtains
The mixed dispersion liquid of even dispersion.Dispersion liquid is taken into flat bottle and carries out slight reduction assembling 20min under the conditions of 85 DEG C；It is cold
But it is put into (- 18 DEG C) freezing 12h of refrigerator lower layer afterwards；After thawing again in 50 DEG C of oil bath pans restore 15h obtain redox graphene/
Hydroxyapatite nano line hydrogel；It is used deionized water dialysis 3 days；By the hydrogel dialysed be put into refrigerator freezing layer (-
18 DEG C) freezing for 24 hours after, at -48 DEG C, vacuum degree 10.0Pa, be freeze-dried 48h, obtain redox graphene/hydroxy-apatite
Stone nano wire aeroge.
It is obtained into graphene-based aeroge in 400 DEG C of carbonization treatment 2.5h (under nitrogen protection).The aeroge is integrally formed
Property is preferable；The aeroge may be implemented quickly to absorb to the contact angle of water up to 145 ° when contacting oil droplet simultaneously, have super oleophylic super
Hydrophobicity, the property of can choose adsorb the waste oil in water, realize the processing of oily waste water, heavy up to itself for the adsorbance of hexadecane
117 times of amount, and circulation absorption ability may be implemented by simply squeezing.
In addition redox graphene/hydroxyapatite nano line aeroge is impregnated in the tannic acid solution of 4mg/mL
After for 24 hours, it is placed on redox graphene/hydroxyapatite nano line that dry 5h in 50 DEG C of vacuum drying ovens obtains hydrophilic surface modification
Aeroge has high adsorptivity to the fluorine ion in water, adsorption capacity reaches 60mg/g with Superhydrophilic.
Embodiment 3: (wherein graphene oxide concentration is configuration 6mL hydroxyapatite nano line/graphene oxide dispersion
5mg/mL, hydroxyapatite nano line concentration are 1mg/mL): it takes the graphene oxide (15mg/mL) of 2mL in beaker, is added
The sodium ascorbate (100mg/mL) of 0.3mL is added in the hydroxyapatite nano line (6mg/mL) of 1mL, and 2.7mL deionization is added
Water carries out ultrasonic disperse (200W/50kHz/120min) to mixed liquor and magnetic agitation (1000rpm/30min) is handled, obtains
Evenly dispersed mixed dispersion liquid.Dispersion liquid is taken into flat bottle and carries out slight reduction assembling 20min under the conditions of 85 DEG C；
10min is rapidly frozen with liquid nitrogen；5h is restored in 70 DEG C of oil bath pans again after thawing to obtain redox graphene/hydroxyapatite and receive
Rice noodles hydrogel；It is used deionized water dialysis 3 days；After the hydrogel dialysed is rapidly frozen 15min with liquid nitrogen, -48 DEG C
Under, vacuum degree 20.0Pa is freeze-dried 48h, obtains redox graphene/hydroxyapatite nano line aeroge.
It is obtained into graphene-based aeroge in 600 DEG C of carbonization treatment 1.5h (under nitrogen protection).The aeroge is integrally formed
Property is preferable；The aeroge can realize quick absorption to oil to the contact angle of water up to 140 ° simultaneously, have super oleophylic super-hydrophobic
Property, the property of can choose adsorbs the waste oil in water, realizes the processing of oily waste water, for chloroform adsorbance up to own wt
110 times, and circulation absorption ability may be implemented by simply squeezing.
In addition by redox graphene/hydroxyapatite nano line aeroge 5mg/mL tetraethyl orthosilicate/second
After impregnating 6h in mixed alkoxide solution, be placed in 35 DEG C of vacuum drying ovens dry 10h obtain the redox graphene of surface hydrophilic modification/
Hydroxyapatite nano line aeroge has high adsorptivity to the fluorine ion in water, adsorption capacity reaches with hydrophily
55mg/g。
Embodiment 4: (wherein graphene oxide concentration is configuration 6mL hydroxyapatite nano line/graphene oxide dispersion
3mg/mL, hydroxyapatite nano line concentration are 1mg/mL): it takes the graphene oxide (18mg/mL) of 1mL in beaker, is added
The hydrazine hydrate (100mg/mL) of 0.3mL is added in the hydroxyapatite nano line (6mg/mL) of 1mL, and 3.7mL deionized water is added,
Ultrasonic disperse (400W/100kHz/60min) and magnetic agitation (1000rpm/30min) processing are carried out to mixed liquor, obtained uniformly
The mixed dispersion liquid of dispersion.Dispersion liquid is taken into flat bottle and carries out slight reduction assembling 2h under the conditions of 60 DEG C；Use liquid nitrogen
It is rapidly frozen 10min；10h is restored in 50 DEG C of oil bath pans again after thawing obtains redox graphene/hydroxyapatite nano line
Hydrogel；It is used deionized water dialysis 3 days；After the hydrogel dialysed is rapidly frozen 15min with liquid nitrogen, at -48 DEG C, very
Reciprocal of duty cycle is 10.0Pa, is freeze-dried 48h, obtains redox graphene/hydroxyapatite nano line aeroge.
It is obtained into graphene-based aeroge in 600 DEG C of carbonization treatment 2h (under argon gas protection).The integrally formed property of the aeroge
Preferably；The aeroge can realize quick absorption to oil to the contact angle of water up to 140 ° simultaneously, have super oleophylic super-hydrophobic
Property, the property of can choose adsorbs the waste oil in water, realizes the processing of oily waste water, for n-hexane adsorbance up to own wt
107 times, and circulation absorption ability may be implemented by simply squeezing.
In addition redox graphene/hydroxyapatite nano line aeroge is soaked in the chitosan solution of 10mg/mL
After steeping for 24 hours, it is placed on redox graphene/hydroxyapatite nano that dry 5h in 50 DEG C of vacuum drying ovens obtains surface hydrophilic modification
Line aeroge has high adsorptivity to the fluorine ion in water, adsorption capacity reaches 75mg/g with Superhydrophilic.
Finally, it is noted that preferred embodiment above is only used to illustrate the technical scheme of the present invention rather than limits, although
The present invention is described in detail by above preferred embodiment, but should be appreciated that can be with by this field staff
Various changes are made to it in the form and details, without departing from claims of the present invention limited range.
Claims (7)
1. a kind of graphene oxide/hydroxyapatite nano line multi-function absorption aeroge preparation method, which is characterized in that packet
Include following steps:
1) GO aqueous dispersions, HAP nano wire aqueous dispersions and chemical reducing agent are mixed in a certain ratio, and stir, ultrasound makes
It is uniformly dispersed；
2) the slight electronation-freezing thawing-drastic reduction process self assembly of dispersion liquid progress will be blended and obtain rGO/HAP water-setting
Glue；
3) above-mentioned hydrogel is successively carried out to freeze-dried and obtains rGO/HAP aeroge；
4) high temperature cabonization processing or surface hydrophilic modification are carried out to above-mentioned aeroge to realize different organic solvents/oil phase or fluorine
The efficient absorption of ion.
2. graphene oxide as described in claim 1/hydroxyapatite nano line multi-function absorption aeroge preparation method,
It is characterized in that, the diameter of hydroxyapatite nano line, between 10~500nm, length is between 1~100 μm, graphite oxide
In 1~10nm, lamella size passes through between hydroxyapatite nano line and graphene oxide the thickness of alkene between 1~10 μm
Hydrogen bond action makes the two have good dispersibility in mixing suspension liquid of aqueous phase.
3. graphene oxide as described in claim 1/hydroxyapatite nano line multi-function absorption aeroge preparation method,
It is characterized in that, the graphene oxide in the step 1) is prepared using Hummers method, the concentration of graphene oxide aqueous dispersions
For 1~20mg/mL；Hydroxyapatite nano line is using calcium oleate presoma-solvent-thermal method preparation, hydroxyapatite nano line water
The concentration of dispersion liquid is 1~15mg/mL；The mass ratio of hydroxyapatite and graphene oxide is 1/15~5；Chemical reducing agent is
Vitamin C, hydrogen iodide, tannic acid, citric acid, ethylenediamine, dopamine, sodium ascorbate, hydrazine hydrate, ammonium hydroxide, thiocarbamide, grape
One of sugar, chitosan, cyclodextrin, sodium hydrogensulfite, vulcanized sodium, hydroquinone or a variety of mixtures, chemical reducing agent with
The mass ratio of graphene oxide is 1/15~10；To mixed dispersion liquid carry out magnetic agitation condition be 150~1500rpm/30~
180min；Ultrasonic treatment condition is 200~750W/25~500kHz/1~120min.
4. graphene oxide as described in claim 1/hydroxyapatite nano line multi-function absorption aeroge preparation method,
It is characterized in that, step 2) the mild or moderate reducing condition is 50~90 DEG C/20min~48h；Freezing conditions are -5 DEG C~-196
DEG C/5min~48h: drastic reduction condition is 50~90 DEG C/20min~48h.
5. graphene oxide as described in claim 1/hydroxyapatite nano line multi-function absorption aeroge preparation method,
It is characterized in that, the step 3) carries out vacuum refrigeration-drying condition are as follows: temperature -30~-55 DEG C, vacuum degree is 5.0~
55Pa, time are 18~72h.
6. graphene oxide as described in claim 1/hydroxyapatite nano line multi-function absorption aeroge preparation method,
It is characterized in that, the step 4) carries out high temperature cabonization condition are as follows: maximum temperature is 400~1000 DEG C, and heating rate is 5~20
DEG C/min, constant temperature time is 30~180min, and required inert atmosphere is one of nitrogen, argon gas, helium, neon.It is hydrophilic to change
Property component can be selected that tetraethyl orthosilicate, chitosan, dopamine, tannic acid, polyethyleneimine etc. be one such or its mixing
Object；Dip-coating, spraying etc. can be used in the mode of hydrophilic modifying；Hydrophilic modifying solution concentration is 0.2~40mg/mL, volume 0.1-
50mL, modification time be 2~for 24 hours.
7. a kind of graphene oxide/hydroxyapatite nano line multi-function using any method preparation of claim 1-6 is inhaled
Attached aeroge.
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| CN111087836A (en) * | 2019-12-16 | 2020-05-01 | 湖南文理学院 | BN/hydroxyapatite nanowire composite heat-conducting insulating flame-retardant thermal interface material |
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| CN114797759B (en) * | 2022-03-29 | 2024-04-02 | 武汉工程大学 | Hydroxyapatite/halloysite nanotube composite adsorption material, and preparation method and application thereof |
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