CN109092259A - A kind of preparation method of functional graphene oxide sponge - Google Patents
A kind of preparation method of functional graphene oxide sponge Download PDFInfo
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Abstract
The present invention synthesizes sulfonated cup [4] aromatic hydrocarbons and GO first, then hydro-thermal reaction is carried out by sulfonated cup [4] aromatic hydrocarbons and graphene oxide and has prepared graphene hydrogel, the aromatic modified 3 D stereo shape graphene oxide sponge (S-GOS) of sulfonated cup [4] is obtained after freeze-drying.Phenetic analysis is carried out to material using analysis means such as SEM, EDS, FT-IR and XRD.By static adsorptive method, influence of the factors such as initial pH value, ionic strength, adsorption time, uranium initial concentration and temperature to S-GOS adsorption uranium (VI) is had studied, and its adsorption dynamics adsorption kinetics and Adsorption thermodynamics are studied.Finally, being investigated to regeneration-reusing of S-GOS adsorption uranium (VI).Synthetic method of the invention is simple, obtains the new material with high surface area and high Supramolecular Recognition and accumulation ability, and absorption property is good, and convenient for recycling, biocompatibility is excellent.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of preparation method of functional graphene oxide sponge.
Background technique
In recent years, as the graphene of two-dimensional material due to its significant and unique property, such as excellent mechanical performance
It is greatly paid close attention to high specific surface area etc. by domestic and foreign scholars.Also there is extensive research in adsorbing domain, but two
It ties up graphene-based adsorbent to be easy to reunite in application, it is not easy to which the problems such as recycling limits its answering in adsorbing separation field
With.Three-dimensional graphite alkenyl macroscopic body has three-dimensional network shape porous structure and large scale, and absorption property is preferably and convenient for collecting back
It receives, has potential application in terms of handling waste water.
Calixarenes is considered as the third generation host molecule after cyclodextrin and crown ether, causes the extensive concern of people.
They can with it is various organic, inorganic and biological guest molecule forms stable host-guest complexation object, and shows macromolecule
Selective and excellent Supramolecular Recognition ability.Strong identification and enrichment function based on calixarenes, target molecule and calixarenes
The selectivity association of hydrophobic cavity has been used to develop different sensor and isolation medium.Wherein cup [4] aromatic hydrocarbons and its derivative
Object suffers from research in many fields, for example, the identification of phase transfer catalyst, supermolecular catalysis, molecular ion, liquid film separation and
Extraction and recovery metal ion etc..Cup [4] aromatic hydrocarbons amide derivatives of the reports such as Shinkai are to uranyl ion (UO2 2+) have very
High compatibility and selectivity.However, since most of calixarenes water solubilitys are poor, using when calixarenes usually in organic solvent
Such as toluene, chloroform uses in methylene chloride etc., brings environmental pollution.Therefore, Water-Soluble Calixarenes (a kind of Calixarene Derivatives)
Become increasingly to be taken seriously in the application.In addition, sulfonated Calixarene Derivatives are good due to it in Water-Soluble Calixarenes
Biocompatibility and synthesis simplicity, be the widest Water-Soluble Calixarenes of research.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of functional graphene oxide sponge, and synthetic method is simple, obtains
The new material with high surface area and high Supramolecular Recognition and accumulation ability is obtained, absorption property is good, convenient for recycling, bio-compatible
Property is excellent.
The technical solution adopted by the present invention is that:
A kind of preparation method of functional graphene oxide sponge, comprising the following steps:
(1) synthesis of sulfonated cup [4] aromatic hydrocarbons
Synthesis to tert-butyl p tertButylcalixarene: p-tert-butylphenol is reacted in NaOH solution with formaldehyde, is obtained to uncle
Butyl cup [4] aromatic hydrocarbons, referred to as product A；
The synthesis of de- tert-butyl p tertButylcalixarene: by product A and anhydrous AlCl3Reaction obtains de- tert-butyl p tertButylcalixarene,
Referred to as product B；
The synthesis of sulfonated cup [4] aromatic hydrocarbons: the de- tert-butyl p tertButylcalixarene (product B) of 1g (2.4mmol) and 10mL is dense
Sulfuric acid mixing, mixed liquor heating stirring at 60 DEG C react 4 hours, completely after reaction, mixed liquor are filtered and is carried out with ether
Obtained solid, is then dried in vacuo at 60 DEG C, can obtain sulfonated cup [4] aromatic hydrocarbons by washing；
(2) preparation of graphene oxide (GO)
Under the conditions of ice-water bath, by 2-3g graphite powder, 1-1.5g NaNO3It is added to the dense H of 45-70mL2SO4In, high-speed stirring
After mixing 30 minutes, 6-9g KMnO is slowly added under conditions of keeping reaction temperature to be lower than 20 DEG C4, ice bath is removed, by solution temperature
35 DEG C are slowly raised to, be slowly added to 80-100mL deionized water after being stirred to react 1h and is gradually heated to 98 DEG C, 30 points of holding
Clock, 30% hydrogen peroxide of 1.5-3mL and 30-50mL deionized water, solution, which is then added, becomes glassy yellow, then filters, gained
Filter cake first uses 5% salt acid elution repeatedly to wash to filtrate close to neutrality, then with a large amount of deionized waters；By washing to neutral oxidation
In water, ultrasonic vibration 1h, centrifuge separation, gained upper liquid is graphene oxide dispersion to graphite ultrasonic disperse, then will
It is dried in vacuo at 60 DEG C, for use；
(3) preparation of the sulfonated aromatic modified graphene oxide sponge of cup [4]: first by 40-50mg GO in 20-30mL
Ultrasonic disperse is uniform in water, sulfonated cup [4] aromatic hydrocarbons of 40-50mg, and ultrasound 10min is then added, then in 160~180
It is reacted in a kettle at DEG C 10~12 hours, after being cooled to room temperature, takes out resulting graphene hydrogel, used deionization
Water washing simultaneously impregnates 48h, then product is freeze-dried to obtain to the graphene sponge S-GOS of functionalization.
Beneficial effects of the present invention:
Water-Soluble Calixarenes are introduced into the surface GO and form nanocomposite by the present invention, their own excellent by combining
Point, and then obtain the new material with high surface area and high Supramolecular Recognition and accumulation ability.
Synthesize sulfonated cup [4] aromatic hydrocarbons and GO first, it is then that sulfonated cup [4] aromatic hydrocarbons and GO is compound, and pass through water
The method of thermal reduction and freeze-drying prepares the aromatic modified graphene oxide sponge (S-GOS) of sulfonated cup [4].The present invention
Middle third step reaction is a hydro-thermal reaction, by heating, pressurizeing, makes the hydroxyl and graphene oxide of sulfonated cup [4] aromatic hydrocarbons
The carboxyl on surface reacts, so that graphene film layer surface will be grafted to sulfonic cup [4] aromatic hydrocarbons.Simultaneously as hydro-thermal
Hydroxyl, the sulfonic fragment for reacting and generating play crosslinked action herein, make to crosslink between graphene oxide layer, from
And the blocky graphene oxide sponge material macroscopic body of three-dimensional for obtaining sulfonic functional.
In addition, S-GOS has good reusability, 13% reduced by only to the adsorbance of uranium after circulation five times.
Detailed description of the invention
The SEM that Fig. 1 is GO and S-GOS schemes, the SEM figure of (a) GO；(b) the SEM figure of S-GOS；(c) S-GOS adsorption uranium
SEM figure；(d) the EDS spectrogram after S-GOS adsorption uranium；
Fig. 2 is the FT-IR spectrogram of GO, S-GOS and S-GOS-U；
Fig. 3 is the XRD spectra of GO and S-GOS；
Fig. 4 is influence of the initial pH to GO and S-GOS adsorption uranium (VI)；
Fig. 5 is influence of the reaction time to GO and S-GOS adsorption uranium (VI)
(GO:pH=5.5；S-GOS:pH=6.0；C0=50mgL-1；V=50mL；T=298.15K)；
Fig. 6 is influence of the initial concentration to GO and S-GOS adsorption uranium (VI)；
Fig. 7 is influence of the temperature to GO and S-GOS adsorption uranium (VI)
(GO:pH=5.5, t=90min；S-GOS:pH=6.0；T=180min；C0=50mgL-1；V=50mL)；
Fig. 8 is the influence that ionic strength adsorbs S-GOS；
Fig. 9 is the reusability of GO and S-GOS.
Specific embodiment
Embodiment 1
A kind of preparation method of functional graphene oxide sponge, comprising the following steps:
(1) synthesis of sulfonated cup [4] aromatic hydrocarbons
Synthesis to tert-butyl p tertButylcalixarene: according to the method for Gutsche etc., p-tert-butylphenol and formaldehyde are existed
It reacts, is obtained to tert-butyl p tertButylcalixarene, referred to as product A in NaOH solution；
The synthesis of de- tert-butyl p tertButylcalixarene: according to the method for Gutsche etc., by product A and anhydrous AlCl3It reacts
To de- tert-butyl p tertButylcalixarene, referred to as product B；
The synthesis of sulfonated cup [4] aromatic hydrocarbons: by de- tertiary fourth cup [4] aromatic hydrocarbons (product B) and the dense sulphur of 10mL of 1g (2.4mmol)
Acid-mixed is closed, and mixed liquor heating stirring at 60 DEG C is reacted 4 hours, completely after reaction, mixed liquor is filtered and is washed with ether
It washs, is then dried in vacuo obtained solid at 60 DEG C, sulfonated cup [4] aromatic hydrocarbons can be obtained；
(2) preparation of graphene oxide (GO)
Under the conditions of ice-water bath, by 2g graphite powder, 1gNaNO3It is added to the dense H of 46mL2SO4In, after high-speed stirred 30 minutes,
6g KMnO is slowly added under conditions of keeping reaction temperature to be lower than 20 DEG C4, ice bath is removed, solution temperature is slowly raised to 35
DEG C, 80mL deionized water is slowly added to after being stirred to react 1h and is gradually heated to 98 DEG C, then holding 30 minutes is added
1.5mL30% hydrogen peroxide and 30mL deionized water, solution become glassy yellow, then filter, and gained filter cake successively uses 5% hydrochloric acid
It is repeatedly washed with deionized water；In water by washing to neutral graphite oxide ultrasonic disperse, ultrasonic vibration 1h, centrifuge separation,
Gained upper liquid is graphene oxide dispersion, is then dried in vacuo it at 60 DEG C, for use；
(3) preparation of the sulfonated aromatic modified graphene oxide sponge of cup [4]: 40mg GO is surpassed in 20mL water first
Sound is uniformly dispersed, and sulfonated cup [4] aromatic hydrocarbons of 40mg, and ultrasound 10min is then added.Reaction flask opening is then placed on reaction
In kettle, reacted 10 hours at 160 DEG C.After being cooled to room temperature, resulting graphene hydrogel is taken out, is washed with deionized
And 48h is impregnated, product is then freeze-dried to obtain graphene sponge S-GOS.
Embodiment 2
A kind of preparation method of functional graphene oxide sponge, comprising the following steps:
(1) synthesis of sulfonated cup [4] aromatic hydrocarbons
Synthesis to tert-butyl p tertButylcalixarene: according to the method for Gutsche etc., p-tert-butylphenol and formaldehyde are existed
It reacts, is obtained to tert-butyl p tertButylcalixarene, referred to as product A in NaOH solution；
The synthesis of de- tert-butyl p tertButylcalixarene: according to the method for Gutsche etc., by product A and anhydrous AlCl3It reacts
To de- tert-butyl p tertButylcalixarene, referred to as product B；
The synthesis of sulfonated cup [4] aromatic hydrocarbons: by de- tertiary fourth cup [4] aromatic hydrocarbons (product B) and the dense sulphur of 10mL of 1g (2.4mmol)
Acid-mixed is closed, and mixed liquor heating stirring at 60 DEG C is reacted 4 hours, completely after reaction, mixed liquor is filtered and is washed with ether
It washs, is then dried in vacuo obtained solid at 60 DEG C, sulfonated cup [4] aromatic hydrocarbons can be obtained；
(2) preparation of graphene oxide (GO)
Under the conditions of ice-water bath, by 3g graphite powder, 1.5g NaNO3It is added to the dense H of 60mL2SO4In, high-speed stirred 30 minutes
Afterwards, 9g KMnO is slowly added under conditions of keeping reaction temperature to be lower than 20 DEG C4, ice bath is removed, solution temperature is slowly raised to
35 DEG C, 100mL deionized water is slowly added to after being stirred to react 1h and is gradually heated to 98 DEG C, then holding 30 minutes is added
3mL30% hydrogen peroxide and 50mL deionized water, solution become glassy yellow, then filter, gained filter cake successively use 5% hydrochloric acid and
Deionized water is repeatedly washed；In water by washing to neutral graphite oxide ultrasonic disperse, ultrasonic vibration 1h, centrifuge separation, institute
Obtaining upper liquid is graphene oxide dispersion, is then dried in vacuo it at 60 DEG C, for use；
(3) preparation of the sulfonated aromatic modified graphene oxide sponge of cup [4]: 50mg GO is surpassed in 30mL water first
Sound is uniformly dispersed, and sulfonated cup [4] aromatic hydrocarbons of 50mg, and ultrasound 10min is then added.Reaction flask opening is then placed on reaction
In kettle, reacted 12 hours at 180 DEG C.After being cooled to room temperature, resulting graphene hydrogel is taken out, is washed with deionized
And 48h is impregnated, product is then freeze-dried to obtain graphene sponge S-GOS.
Adsorption experiment and performance test (by taking object is made in embodiment 1 as an example)
It is utilized respectively GO and S-GOS and has carried out uranium absorption experiment, and the performance of absorption front and back is tested.
(1) adsorption experiment
1) preparation of solution
1mg·mL-1The preparation of uranium standard reserving solution: 0.5896g U is accurately weighed3O8In 50mL beaker, 2.5mL is added
After aqua regia dissolution then heating evaporation stops heating, naturally cools to room temperature, be transferred to after 5mL concentrated hydrochloric acid is added to wet salt
In 500mL volumetric flask, constant volume is shaken up, and solution concentration is 1mgmL at this time-1.The uranium standard solution of various concentration can use this standard
Stock solution dilutes to obtain.
Arsenazo Ⅲ solution (ρ=0.5gL-1) preparation: accurately weigh 0.250g arsenazo Ⅲ, dissolved with water, then
It is transferred in 500mL volumetric flask, constant volume shakes up.
The preparation of monoxone-sodium acetate buffer (pH=2.50): with water by the monoxone ultrasonic dissolution of 47.25g,
Constant volume obtains 0.5molL in the volumetric flask of 1000mL-1Chloroacetic acid solution；10.25g sodium acetate is dissolved with water, in 250mL
Constant volume obtains 0.5molL in volumetric flask-1Sodium acetate solution.Then it pipettes 250mL chloroacetic acid solution and 150mL sodium acetate is mixed
Close, with pH meter adjust pH be 2.50 to get arrive required buffer liquid.
2) adsorption experiment
Uranium (VI) solution is adjusted to certain pH value with prepared NaOH and HCl solution, is accurately pipetted 50mL and has been mixed up pH
Uranium (VI) solution in 150mL stuffed conical flask.10mg GO or 5mg S-GOS (two comparative experimentss) is added thereto.So
Afterwards conical flask is placed in vibrate at desired temperatures in oscillator and be taken out after a certain period of time, with Suction filtration device by adsorbent and solution
The S-GOS-U of isolated filtrate and adsorption uranium, using the concentration of uranium (VI) in arsenazo III method measurement filtrate, according to formula
(1) adsorption capacity is calculated.
C in formula0It is uranium (VI) ion concentration before absorption, mgL-1；CeIt is that uranium (VI) ion after absorption in filtrate is dense
Degree, mgL-1；V is the volume of solution, L；M is the quality of adsorbent, g.
Distribution coefficient Kd(mL·g-1) calculated by formula (2):
Ce: the concentration of solution, mgL when adsorption equilibrium-1, qe: adsorbance when balance, mgg-1。
(2) performance test and interpretation of result
1) SEM phenetic analysis
In Fig. 1, (a), (b) are respectively the SEM figure of GO and S-GOS.It can be seen that GO is with fold from Fig. 1 (a)
Bidimensional laminated structure, Fig. 1 (b) shows that S-GOS has loose porous network-like structure, and the loose porous structure of S-GOS promotees
It is diffused into 3D structure into metal ion, is more advantageous to it and is adsorbed.In addition, it has certain mechanical strength (such as Fig. 1 again
(b) cylindrical body that 2 diameters are about 1cm shown in illustration 2 can bear the weight of 50g counterweight, and benefit can be recycled when as adsorbent
It is strong with property.
As shown in Fig. 1 (c), the S-GOS after absorption U (VI) maintains original pattern, illustrates the structural stability of S-GOS
Preferably.
In order to be better understood by absorption situation of the U (VI) on S-GOS, EDS has been carried out to the S-GOS after adsorption uranium (VI)
Analysis.As shown in Fig. 1 (d), occur the characteristic peak of U element in EDS spectrogram, illustrates that there is the presence of uranium on the surface of S-GOS.It is composing
Do not occur S element in figure, may is that because the detection limit of EDS is not achieved in S constituent content very little.
2) FT-IR phenetic analysis
Fig. 2 is the infrared spectrum of GO and S-GOS.Wherein, in the infrared spectrum of GO, 3275cm-1, 1721cm-1,
1624cm-1And 1040cm-1The absorption peak that place occurs is respectively the stretching vibration peak of O-H, C=O, C=C and C-O.S-GOS's
In spectrogram, compared with GO, the absorption peak of oxygen-containing functional group obviously weakens, and illustrates that it is anti-that reduction has occurred in the part GO in water-heat process
It answers.In 1204cm-1The new absorption peak that place occurs is-SO2Stretching vibration caused by, this demonstrate sulfonated cup [4] aromatic hydrocarbons
It is reacted in water-heat process with GO.
For the infrared spectroscopy after S-GOS adsorption uranium (VI), in 922cm-1There is new absorption peak in place, this is attributed to [O=
UVI=O]2+Antisymmetric vibration.In addition ,-SO2Absorption peak red shift has occurred, this may be uranium (VI) absorption caused by.
3) XRD characterization is analyzed
The XRD spectra of GO and S-GOS is as shown in Figure 3.As seen from the figure, GO 2 θ=10.6 ° characteristic diffraction peak (001) very
Sharply, peak intensity is larger, illustrates that the graphene oxide crystallinity of preparation is higher.And S-GOS disappears in 2 θ for the peak at 10.6 ° completely
It loses, and occurs the lesser wide diffraction maximum of an intensity at 24 ° or so, compared with GO, 2 θ become larger, this is because also by hydro-thermal
After original reaction, the piece interlamellar spacing of S-GOS becomes smaller, and the skeleton of S-GOS is made of the graphene film of unordered stacking.
4) influence of the initial pH value to absorption
Influence of the pH to GO and S-GOS adsorption uranium (VI) is very big as can be seen from Figure 4.As pH increases to 6.0 left sides from 3.0
The right side, GO and S-GOS are gradually increased the adsorbance of uranium U (VI), they reach maximum in pH=5.5 and pH=6.0 or so respectively,
Subsequent adsorbance is held essentially constant.From fig. 4, it can be seen that in aqueous solution, U (VI) shows difference with the variation of pH
Existence form.In pH < 6, uranium (VI) is mainly with UO2 2+、UO2OH+(UO2)3(OH)5+Form exist.In lower pH
Under value, the H of high concentration+Meeting and UO2 2+The active site on competitive adsorbate surface.On the other hand, adsorbent surface when low ph value
Hydrone and active function groups are easy protonation and generate positively charged surface, generate electrostatic between positively charged uranium (VI)
Repulsive force is also unfavorable for the absorption of uranium (VI), smaller so as to cause adsorbance.However as the increase of pH, H in solution+Concentration
Gradually reduce, the competitive Adsorption effect with U (VI) also dies down therewith.Meanwhile the H of covering3O+By deprotonation and in adsorbent
Surface leaves more active sites, and also deprotonation increases the negative electrical charge on its surface to the active group of adsorbent surface, from
And enhance the electrostatic attraction between adsorbent and uranium (VI), it eventually leads to adsorbent and the adsorbance of uranium (VI) is gradually increased.When
When pH > 6, positively charged uranium (VI) is gradually reduced, electronegative gradually to increase, and is unfavorable for the absorption of uranium (VI), and solution
In UO is gradually precipitated3·2H2O precipitating.So the Optimal pH of GO and S-GOS adsorption uranium is respectively 5.5 and 6.0, and for subsequent
In adsorption experiment.
5) adsorption dynamics adsorption kinetics research
Influence of the adsorption time to S-GOS and GO absorption U (VI) is as shown in Figure 5.As seen from the figure, in the preceding 50min of beginning,
S-GOS and GO is significant to the adsorption effect of uranium U (VI).With the increase of adsorption time, the rate of two kinds of adsorbent absorption U (VI)
It slowly reduces, finally reaches adsorption equilibrium in 180min and 90min or so respectively.In subsequent adsorption experiment, S-GOS and GO
Adsorption time be set to 180min and 90min.
6) the influence research of initial concentration
Influence of the uranium initial concentration to GO and S-GOS adsorption uranium (VI) performance is as shown in Figure 6.It can be seen from the figure that uranium
(VI) adsorbance on GO and S-GOS increases with the increase of uranium initial concentration.When uranium initial concentration is greater than 60mgL-1When,
Adsorbance of the uranium (VI) on GO is held essentially constant；When uranium initial concentration is greater than 70mgL-1When, uranium (VI) is on S-GOS
Absorption is held essentially constant.
7) Adsorption thermodynamics research
Within the scope of 15~55 DEG C of temperature, influence of the research temperature to GO and S-GOS absorption U (VI).As shown in fig. 7, uranium
(VI) adsorbance on GO and S-GOS increases with the raising of solution temperature, this shows that the temperature for increasing solution is conducive to U
(VI) absorption.
8) influence of the ionic strength to absorption
Since solution ion strength can change the electrostatic interaction between adsorbent surface and adsorbate ion, so
It might have influence to the adsorption capacity of target metal ions.In view of various electrolysis present in nuke rubbish and environmental sample
Matter, the influence factor for selecting NaCl to adsorb as ionic strength to uranium (VI).As shown in figure 8, with the increase of NaCl concentration, uranium
(VI) adsorbance decline.The reduction of adsorbance may be due to UO2 2+It is formd between the active site on adsorbent surface
Outer layer compound illustrates the control that the absorption of uranium (VI) is complexed by superficies by S-GOS.Therefore, the Na of addition+Competitive Adsorption
Site limits the further absorption of uranium (VI).
9) desorption and reusability
Reusable property is to evaluate an importance of performance of the adsorbent quality.In this experiment, in order to study GO
With the reusability of S-GOS, using 1.0molL-1Strippant of the HCl solution as GO and S-GOS.It can from Fig. 9
Out, 1.0molL-1HCl solution is preferable to the desorption effect of uranium (VI), and desorption efficiency is up to 98% or so.GO and S-GOS are used for
Continuous adsorption/desorption is recycled to assess the reusability of adsorbent.It can be observed from figure, after circulation 5 times, GO is to uranium
(VI) adsorbance is from 148mgg-1It is reduced to 108.9mgg-1(reducing 26%), and S-GOS to the adsorbance of uranium from
241mg·g-1It is reduced to 210mgg-1(reducing 13%).This demonstrate S-GOS to have good reusability.
Brief summary
Spread out using scanning electron microscope (SEM), X-ray energy spectrometer (EDS), Fourier infrared spectrum (FT-IR) and x-ray powder
It penetrates instrument (XRD) to analyze its pattern and composition, analysis is the result shows that GO and sulfonated cup [4] aromatic hydrocarbons are sent out under hydrothermal conditions
Raw cross-linking reaction is assembled into three-dimensional grapheme macroscopic body.The material is with loose porous network-like structure and has centainly
Mechanical strength and fixed profile are conducive to adsorbing metal ions and convenient for recycling.
Initial pH value of the S-GOS and GO to the absorption of uranium (VI) by solution, the shadow of adsorption time, uranium initial concentration and temperature
It rings.Ionic strength also influences absorption of the S-GOS to uranium (VI) simultaneously, illustrates what S-GOS adsorption uranium (VI) was complexed by superficies
Control.
GO and L-Ar-GOS meets Langmuir adsorption isotherm model to the absorption of uranium (VI), and S-GOS is to uranium (VI)
Monolayer adsorption amount is 257.07mgg-1, it is higher than GO (192.68mgg-1), illustrate that the adsorption capacity ratio GO of S-GOS is strong.GO and
S-GOS is a heat absorption and spontaneous process to the absorption of uranium (VI).In addition, 1.0molL-1HCl solution is to uranium (VI)
Desorption effect is preferable, and S-GOS has good reusability, reduced by only 13% to the adsorbance of uranium after circulation five times.
Claims (1)
1. a kind of preparation method of functional graphene oxide sponge, which comprises the following steps:
(1) synthesis of sulfonated cup [4] aromatic hydrocarbons
Synthesis to tert-butyl p tertButylcalixarene: p-tert-butylphenol is reacted in NaOH solution with formaldehyde, is obtained to tert-butyl
Cup [4] aromatic hydrocarbons, referred to as product A；
The synthesis of de- tert-butyl p tertButylcalixarene: by product A and anhydrous AlCl3Reaction obtains de- tert-butyl p tertButylcalixarene, referred to as produces
Object B；
The synthesis of sulfonated cup [4] aromatic hydrocarbons: product B and the 10mL concentrated sulfuric acid of 1g is mixed, mixed liquor heating stirring at 60 DEG C
Reaction 4 hours, completely reaction after, by mixed liquor filter and washed with ether, then by obtained solid at 60 DEG C vacuum
It is dry, sulfonated cup [4] aromatic hydrocarbons can be obtained；
(2) preparation of graphene oxide
Under the conditions of ice-water bath, by 2-3g graphite powder, 1-1.5g NaNO3It is added to the dense H of 45-70mL2SO4In, high-speed stirred 30
After minute, 6-9g KMnO is slowly added under conditions of keeping reaction temperature to be lower than 20 DEG C4, ice bath is removed, solution temperature is slow
35 DEG C are increased to, be slowly added to 80-100mL deionized water after being stirred to react 1h and is gradually heated to 98 DEG C, is kept for 30 minutes, so
30% hydrogen peroxide of 1.5-3mL and 30-50mL deionized water, solution are added afterwards becomes glassy yellow, then filters, gained filter cake
First repeatedly washed with 5% salt acid elution to filtrate close to neutrality, then with a large amount of deionized waters；By washing to neutral graphite oxide
Ultrasonic disperse in water, ultrasonic vibration 1h, centrifuge separation, gained upper liquid is graphene oxide dispersion, then by its
It is dried in vacuo at 60 DEG C, for use；
(3) preparation of the sulfonated aromatic modified graphene oxide sponge of cup [4]: first by 40-50mg GO in 20-30mL water
Ultrasonic disperse is uniform, sulfonated cup [4] aromatic hydrocarbons of 40-50mg, and ultrasound 10min is then added, then at 160~180 DEG C
It reacts 10~12 hours in a kettle, after being cooled to room temperature, takes out resulting graphene hydrogel, be washed with deionized water
48h is washed and impregnated, then product is freeze-dried to obtain to the graphene sponge S-GOS of functionalization.
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| CN112624092A (en) * | 2021-01-13 | 2021-04-09 | 北京大学 | Amidated graphene aerogel and preparation method and application thereof |
| CN112871145A (en) * | 2021-01-13 | 2021-06-01 | 北京大学 | Graphene material and preparation method and application thereof |
| CN115445567A (en) * | 2022-09-16 | 2022-12-09 | 浙江大学 | Method for efficiently adsorbing uranium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112624092A (en) * | 2021-01-13 | 2021-04-09 | 北京大学 | Amidated graphene aerogel and preparation method and application thereof |
| CN112871145A (en) * | 2021-01-13 | 2021-06-01 | 北京大学 | Graphene material and preparation method and application thereof |
| CN112871145B (en) * | 2021-01-13 | 2022-05-13 | 北京大学 | Graphene material and preparation method and application thereof |
| CN115445567A (en) * | 2022-09-16 | 2022-12-09 | 浙江大学 | Method for efficiently adsorbing uranium |
| CN115445567B (en) * | 2022-09-16 | 2023-11-28 | 浙江大学 | Method for efficiently adsorbing uranium |
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