CN108129868B - Method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquid - Google Patents
Method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquid Download PDFInfo
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Abstract
A method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor belongs to the field of graphene oxide/cellulose composite materials. The GO mixed acid liquid is prepared by an improved Hummers method; pretreating lignocellulose; preparation of GO/cellulose composite: and (2) adding the prepared lignocellulose into the GO mixed acid solution prepared in the step (1), heating for reaction, washing, filtering and dialyzing to be neutral, and freeze-drying or carrying out ultrasonic treatment on the obtained mixed solution and then freeze-drying to obtain the GO/cellulose composite material. The invention provides a method for preparing a GO/cellulose composite material by directly utilizing an acidic mixed solution obtained after a Hummers method reaction. The method simplifies the operation of preparing the GO/cellulose composite material, shortens the reaction time, saves the preparation cost, and can reduce the influence on the environment to a certain extent.
Description
Technical Field
The invention belongs to the field of graphene oxide/cellulose composite materials; in particular to a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor.
Background
Graphene Oxide (GO) is used as an important oxygen-containing derivative of Graphene, and a large number of oxygen-containing functional groups such as carboxyl, hydroxyl, epoxy and the like exist on the surface and the edge of the GO, so that the GO is easily dispersed in various solvents, and the possibility is provided for compounding the GO with other substances, and the current Hummers method is one of important methods for preparing GO.
Cellulose is a renewable, degradable, environmentally friendly material. In recent years, a great number of researchers have made GO and cellulose into composite materials, and such composite materials are expected to be applied in the fields of adsorption, electromagnetic shielding, electrochemistry, and the like. Most researchers in these studies have prepared pure GO and nanocellulose separately, and then mixed in a solvent for complex preparation. When GO is prepared by using the Hummers method, a large amount of residual acidic solution is generated, which causes negative effects on the environment and waste of medicaments, and in addition, the washing and filtering are not easy to operate no matter pure GO or cellulose is prepared, the dialysis time is long, and the cost is high.
Disclosure of Invention
The invention aims to provide a method for directly preparing a GO/cellulose composite material by using a Hummers method mixed acid solution.
The invention is realized by the following technical scheme:
a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor comprises the following steps:
step a, preparing GO mixed acid liquid by using an improved Hummers method;
step b, extracting wood powder;
step c, pretreating lignocellulose by using the wood powder extracted in the step b;
step d, preparing the GO/cellulose composite material: and (c) adding the pretreated lignocellulose obtained in the step (c) into the GO mixed acid solution prepared in the step (a), heating for reaction, washing, filtering and dialyzing to be neutral, and freeze-drying or carrying out ultrasonic treatment on the obtained mixed solution and then freeze-drying to obtain the GO/cellulose composite material.
The invention relates to a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor, which comprises the following steps:
step a1, weighing 55-60 ml of 98% concentrated sulfuric acid in a beaker, placing the beaker in an ice water bath, cooling the beaker to 2-5 ℃, and adding 2.5g of graphite powder and 1.25g of NaNO under the stirring condition3And 7.5g KMnO was added slowly4Keeping the reaction temperature below 10 ℃ and reacting for 90min to obtain a mixed solution for later use;
step a2, placing the mixed solution obtained in the step a1 in a warm water bath, controlling the reaction temperature to be 30-40 ℃ under the stirring condition, and reacting for 30-40 min to obtain a mixed solution for later use;
step a3, dropwise adding and concentrating under the condition of stirringControlling the reaction temperature of deionized water with the same volume as sulfuric acid to be 90-100 ℃, reacting for 15-25 min, and then adding 30% H2O2And adding the mixture into the mixed solution until no obvious bubbles are generated to obtain GO mixed acid solution, wherein the solution turns golden yellow, but no washing and filtering operation is performed on the solution. Magnetic stirring was used throughout the experiment.
The invention relates to a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor, which comprises the following steps:
step b1, mixing the raw materials in a volume ratio of 2: 1, weighing benzene and an absolute ethyl alcohol solution, and uniformly mixing for later use;
step b2, weighing a certain amount of wood powder, and drying the wood powder until the wood powder is absolutely dry for use;
b3, adding the mixed solution obtained in the step b1 into a 150ml soxhlet extractor, wherein the adding amount is 150-170 ml, then wrapping 3g of the wood flour prepared in the step b2 with filter paper, placing the wrapped wood flour into the bottom of the soxhlet extractor, controlling the reflux speed for 4 times/h, and extracting for 6h to obtain a product for later use;
and b4, drying the product prepared in the step b3 to obtain the extracted wood powder.
According to the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid liquor, the heating temperature in the step b3 is 90 ℃.
The invention relates to a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor, which comprises the following steps:
step c1, adding 65ml of distilled water, 0.6g of sodium chlorite, 0.5ml of glacial acetic acid and 2g of the extracted wood flour prepared in the step b into a conical flask, uniformly mixing, treating in a water bath at 75 ℃ for 1 hour, then adding 0.6g of sodium chlorite and 0.5ml of glacial acetic acid, continuing to treat at 75 ℃ for 1 hour, and repeating the steps for 4-6 times to obtain a mixed solution for later use;
step c2, sucking and filtering the mixed solution obtained in the step c1, washing the mixed solution to be neutral by using distilled water, placing the obtained product into a 4% NaOH solution, and treating the product at 90 ℃ for 2 hours to obtain a mixed solution for later use;
and c3, sucking and filtering the mixed solution obtained in the step c2, washing the mixed solution with distilled water to be neutral, and drying the obtained product to obtain the pretreated lignocellulose.
The method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid liquor has the advantage that the temperature of the oven in the step c3 is 60 ℃.
The invention relates to a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor, which comprises the steps of adding 0.5g of lignocellulose prepared in the step 3 into 20ml of GO mixed acid liquor prepared in the step 1, heating and reacting in a water bath at 45 ℃, and reacting for 2h under the condition of magnetic stirring.
The invention relates to a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor, which comprises the following steps of washing, filtering and dialyzing until the neutral state is heating reaction, adding 150ml of deionized water, stirring uniformly, standing for 12h, removing supernatant, filtering a lower layer mixture by using a sand core funnel and a 0.45 mu m cellulose acetate microporous filter membrane, diluting substances on the filter membrane by using deionized water, then putting into a dialysis bag for dialysis until no precipitate is detected by using barium chloride solution, and detecting by using a PH test paper until the neutral state is detected.
The invention relates to a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor, wherein in the step d, ultrasonic treatment is carried out at an ultrasonic power of 420W for 30min, and the temperature is controlled to be about 20 ℃.
The invention discloses a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquid, and provides a method for directly preparing GO/cellulose composite material by using acid mixed liquid obtained after reaction of the Hummers method without filtering and dialyzing GO. The method simplifies the operation of preparing the GO/cellulose composite material, shortens the reaction time, saves the preparation cost, fully utilizes the sulfuric acid in the reaction liquid, and can reduce the influence on the environment to a certain extent.
Compared with the existing GO/cellulose composite material preparation method, the method has the following advantages: (1) pure GO does not need to be separated out by filtration; (2) directly putting lignocellulose into an acid solution containing GO to prepare a GO/cellulose composite material; the reaction time is shortened, the preparation cost is saved, the sulfuric acid in the reaction liquid is fully utilized, and the influence on the environment can be reduced to a certain extent.
Drawings
FIG. 1 is an XRD contrast spectrum of a GO/cellulose composite prepared by a method according to one embodiment;
FIG. 2 is an infrared contrast spectrum of a GO/cellulose composite prepared by the method of embodiment two;
FIG. 3 is a macro-contrast photograph of GO/cellulose composite made by one embodiment of the method at different times.
Detailed Description
The first embodiment is as follows:
a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor comprises the following steps:
step a, preparing GO mixed acid liquid by using an improved Hummers method;
step b, extracting wood powder;
step c, pretreating lignocellulose by using the wood powder extracted in the step b;
step d, preparing the GO/cellulose composite material: and (c) adding the pretreated lignocellulose obtained in the step (c) into the GO mixed acid liquid prepared in the step (a), heating for reaction, washing, filtering and dialyzing to be neutral, carrying out ultrasonic treatment on the obtained mixed liquid, and carrying out freeze drying on the obtained mixed liquid to obtain the GO/cellulose composite material.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, step a includes the following steps:
step a1, weighing 55ml of concentrated sulfuric acid with the concentration of 98 percent in a beaker, placing the weighed concentrated sulfuric acid in an ice-water bath to cool the concentrated sulfuric acid to 4 ℃, and adding 2.5g of graphite powder and 1.25g of NaNO under the condition of stirring3And 7.5g KMnO was added slowly4Keeping the reaction temperature below 10 ℃ and reacting for 90min to obtain a mixed solution for later use;
step a2, placing the mixed solution obtained in the step a1 in a warm water bath, controlling the reaction temperature to be 35 ℃ under the stirring condition, and reacting for 30min to obtain a mixed solution for later use;
step a3, dropwise adding deionized water with the same volume as concentrated sulfuric acid under the stirring condition, controlling the reaction temperature to be 95 ℃, reacting for 15min, and then adding 30% H2O2And adding the mixture into the mixed solution until no obvious bubbles are generated to obtain the GO mixed acid solution.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, step b includes the following steps:
step b1, mixing the raw materials in a volume ratio of 2: 1, weighing benzene and an absolute ethyl alcohol solution, and uniformly mixing for later use;
step b2, weighing a certain amount of wood powder, and drying the wood powder until the wood powder is absolutely dry for use;
b3, adding the mixed solution obtained in the step b1 into a 150ml Soxhlet extractor, wherein the adding amount is 170ml, then wrapping 3g of the wood flour prepared in the step b2 by using filter paper, placing the wrapped wood flour into the bottom of the Soxhlet extractor, controlling the reflux speed for 4 times/h, and extracting for 6h to obtain a product for later use;
and b4, drying the product prepared in the step b3 to obtain the extracted wood powder.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the heating temperature in the step b3 is 90 ℃.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, step c includes the following steps:
step c1, adding 65ml of distilled water, 0.6g of sodium chlorite, 0.5ml of glacial acetic acid and 2g of the extracted wood flour prepared in the step b into a conical flask, uniformly mixing, treating in a water bath at 75 ℃ for 1 hour, then adding 0.6g of sodium chlorite and 0.5ml of glacial acetic acid, continuing to treat at 75 ℃ for 1 hour, and repeating the steps for 4-6 times to obtain a mixed solution for later use;
step c2, sucking and filtering the mixed solution obtained in the step c1, washing the mixed solution to be neutral by using distilled water, placing the obtained product into a 4% NaOH solution, and treating the product at 90 ℃ for 2 hours to obtain a mixed solution for later use;
and c3, sucking and filtering the mixed solution obtained in the step c2, washing the mixed solution with distilled water to be neutral, and drying the obtained product to obtain the pretreated lignocellulose.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the temperature of the oven in the step c3 is 60 ℃.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, 0.5g of the lignocellulose prepared in the step 3 is added into 20ml of the GO mixed acid solution prepared in the step 1 in the step d, and the heating reaction is carried out by placing the mixture in a water bath at 45 ℃ and reacting for 2 hours under the magnetic stirring condition.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, after heating reaction, washing, filtering and dialyzing until the mixture is neutral, adding about 150ml of deionized water, stirring uniformly, standing for 12 hours, removing a supernatant, filtering a lower layer mixture by using a sand core funnel and a 0.45 mu m cellulose acetate microporous filter membrane, diluting substances on the filter membrane by using the deionized water, then putting the diluted substances into a dialysis bag, dialyzing until no precipitate is detected by using a barium chloride solution, and detecting the substances to be neutral by using a pH test paper.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the ultrasonic treatment in the step d is performed at an ultrasonic power of 420W for 30min, and the temperature is controlled to be about 20 ℃.
In the embodiment, as shown in fig. 1, the XRD comparison patterns of GO/cellulose composite material (U-GO/C) prepared by the method of directly preparing GO/cellulose composite material by using Hummers method mixed acid solution, GO/cellulose composite material (GO/C) prepared by direct freeze-drying method, pure GO material (U-GO) prepared by ultrasonic method, pretreated pure GO material (GO), and pretreated lignocellulose are shown in fig. 1, where pure GO has a strong diffraction characteristic peak at 2 θ ═ 11.7 °, corresponding to (001) crystal face of graphene oxide, and the Bragg formula can estimate that the interlayer spacing is 0.75nm, and a weak peak at 2 θ ═ 26.5 °, the interlayer spacing is 0.33nm, corresponding to (002) crystal face of graphite, which may be caused by the prepared graphene oxide being re-stacked, after the GO sample is subjected to ultrasonic treatment, the diffraction peak of the U-GO sample at 26.5 degrees does not exist, while the diffraction peak of the (001) crystal face is still at 11.7 degrees, but the intensity of the peak is reduced. These results demonstrate that the present process successfully produces GO with a large number of monolayer structures. XRD diffraction peaks of pretreated lignocellulose appear at two positions of 16 degrees and 22.6 degrees, corresponding to 110 crystal planes and 200 crystal planes respectively, and belong to a cellulose I-type crystal structure.
The reason why the XRD spectrum of GO/C shows a broad dispersion peak at 22.6 ° in addition to the characteristic GO diffraction peak at about 11.7 ° 2 θ, which corresponds to the characteristic peak of 200 crystal plane of lignocellulose, but the characteristic peak of 110 crystal plane of lignocellulose at about 16 ° is not obvious, may be that the addition amount of lignocellulose is relatively small, and during hydrolysis, lignocellulose is more in GO in a dispersed amorphous state, so the crystallinity of cellulose is relatively low, and the strength of the characteristic peak is not high.
The XRD atlas of two samples U-GO/C and U-GO after ultrasonic treatment shows that although the sample U-GO keeps the characteristic peak of GO at 2 theta (11.7 degrees), the peak intensity ratio GO is obviously reduced, the crystallinity is greatly reduced, and the analysis reason is that the crystallinity is reduced due to the fact that the GO sheet layer is broken due to overlarge ultrasonic power or overlong ultrasonic time. And the same ultrasonic power and ultrasonic treatment time U-GO/C keep the characteristic peak of GO/C at the position of 11.7 degrees 2 theta, the peak intensity is reduced compared with GO/C, the crystallinity is reduced to some extent, but the contrast is not very strong, because the cellulose in the composite material is uniformly dispersed in the GO sheet layer, and the cellulose plays a role in protecting the GO sheet layer under the ultrasonic action.
The second embodiment is as follows:
a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor comprises the following steps:
step a, preparing GO mixed acid liquid by using an improved Hummers method;
step b, extracting wood powder;
step c, pretreating lignocellulose by using the wood powder extracted in the step b;
step d, preparing the GO/cellulose composite material: and (c) adding the pretreated lignocellulose obtained in the step (c) into the GO mixed acid solution prepared in the step (a), heating for reaction, washing, filtering and dialyzing to be neutral, and freeze-drying the obtained mixed solution to obtain the GO/cellulose composite material.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, step a includes the following steps:
step a1, weighing 55ml of concentrated sulfuric acid with the concentration of 98 percent in a beaker, placing the weighed concentrated sulfuric acid in an ice-water bath to cool the concentrated sulfuric acid to 4 ℃, and adding 2.5g of graphite powder and 1.25g of NaNO under the condition of stirring3And 7.5g KMnO was added slowly4Keeping the reaction temperature below 10 ℃ and reacting for 90min to obtain a mixed solution for later use;
step a2, placing the mixed solution obtained in the step a1 in a warm water bath, controlling the reaction temperature to be 35 ℃ under the stirring condition, and reacting for 30min to obtain a mixed solution for later use;
step a3, dropwise adding deionized water with the same volume as concentrated sulfuric acid under the stirring condition, controlling the reaction temperature to be 95 ℃, reacting for 15min, and then adding 30% H2O2And adding the mixture into the mixed solution until no obvious bubbles are generated to obtain the GO mixed acid solution.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, step b includes the following steps:
step b1, mixing the raw materials in a volume ratio of 2: 1, weighing benzene and an absolute ethyl alcohol solution, and uniformly mixing for later use;
step b2, weighing a certain amount of wood powder, and drying the wood powder until the wood powder is absolutely dry for use;
b3, adding the mixed solution obtained in the step b1 into a 150ml Soxhlet extractor, wherein the adding amount is 170ml, then wrapping 3g of the wood flour prepared in the step b2 by using filter paper, placing the wrapped wood flour into the bottom of the Soxhlet extractor, controlling the reflux speed for 4 times/h, and extracting for 6h to obtain a product for later use;
and b4, drying the product prepared in the step b3 to obtain the extracted wood powder.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the heating temperature in the step b3 is 90 ℃.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, step c includes the following steps:
step c1, adding 65ml of distilled water, 0.6g of sodium chlorite, 0.5ml of glacial acetic acid and 2g of the extracted wood flour prepared in the step b into a conical flask, uniformly mixing, treating in a water bath at 75 ℃ for 1 hour, then adding 0.6g of sodium chlorite and 0.5ml of glacial acetic acid, continuing to treat at 75 ℃ for 1 hour, and repeating the steps for 4-6 times to obtain a mixed solution for later use;
step c2, sucking and filtering the mixed solution obtained in the step c1, washing the mixed solution to be neutral by using distilled water, placing the obtained product into a 4% NaOH solution, and treating the product at 90 ℃ for 2 hours to obtain a mixed solution for later use;
and c3, sucking and filtering the mixed solution obtained in the step c2, washing the mixed solution with distilled water to be neutral, and drying the obtained product to obtain the pretreated lignocellulose.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the temperature of the oven in the step c3 is 60 ℃.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, 0.5g of the lignocellulose prepared in the step 3 is added into 20ml of the GO mixed acid solution prepared in the step 1 in the step d, and the heating reaction is carried out by placing the mixture in a water bath at 45 ℃ and reacting for 2 hours under the magnetic stirring condition.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, after heating reaction, washing, filtering and dialyzing until the mixture is neutral, adding about 150ml of deionized water, stirring uniformly, standing for 12 hours, removing a supernatant, filtering a lower layer mixture by using a sand core funnel and a 0.45 mu m cellulose acetate microporous filter membrane, diluting substances on the filter membrane by using the deionized water, then putting the diluted substances into a dialysis bag, dialyzing until no precipitate is detected by using a barium chloride solution, and detecting the substances to be neutral by using a pH test paper.
In the method for directly preparing GO/cellulose composite material by using Hummers method mixed acid solution according to the embodiment, the infrared contrast spectra of the prepared GO/cellulose composite material (GO/C), the pretreated pure GO material (GO) and the pretreated lignocellulose are shown in fig. 2:
as can be seen from FIG. 2, the pretreated pure GO material (GO) is at 3360cm-1Nearby strong broad peak belongs to the stretching vibration peak of O-H, 1730cm-1、1398cm-1、1224cm-1And 1056cm-1Then belong to the characteristic peaks of-COOH, C-OH, C-O-C and C-OH bonds, respectively, 1624cm-1The characteristic peak of (a) belongs to the C ═ C bond.
The infrared spectrum of the pretreated lignocellulose in FIG. 2 clearly shows the spectral characteristics of the cellulose, wherein 3334cm-1、2894cm-1Corresponding to stretching vibrations of-OH and-CH, respectively, 1428cm-1And 1368cm-1Bending vibrations attributed to-CH 2 and-CH, respectively, of 1030cm-1And 1160cm-1Two peaks of (a) are characteristic oscillation peaks of C-OH, 896cm-1The point corresponds to deformation vibration of-CH. 1460cm cannot be found in the map-1Nearby characterization of-CH in lignin2The absorption peak of deformation vibration indicates that the lignin side chain has been degraded, 1630cm-1The sum of the absorption peak of C ═ O stretching vibration on the side chain of the lignin is represented as 1500-1600 cm-1The absorption peaks that characterize the stretching vibration of the benzene ring skeleton structure become less obvious to indicate that most of the lignin is removed from the pretreated lignocellulose. 1734cm-1The stretching vibration absorption peak nearby representing the chromophoric group C ═ O of the hemicellulose xylopoly basically disappears in the spectrogram, and is 1614cm-1The characteristic absorption peak of C ═ O still appears, the intensity is weaker, most of hemicellulose is removed, and a small amount of hemicellulose still remains.
The infrared spectrum of the GO/C composite material is shown in figure 2, 3330cm-1The nearby strong broad peak belongs to the-OH absorption peak in the composite, and 1626cm-1、1422cm-1、1234cm-1And 1054cm-1The absorption peaks in (a) are respectively attributed to the characteristic peaks of-COOH, C ═ C bond, and C-O-C, C-OH group in the composite material. Different from GO/NCC composite material prepared under alkaline condition, the invention is 1734cm in length because the GO/NCC composite material is prepared in acidic solution-1The characteristic peak of the-COOH group at the site was not clearly observed but was preserved.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the macro-contrast photos of the prepared GO/cellulose composite material (GO/C) at different time are shown in fig. 3, and it can be seen from fig. 3 that the freeze-dried composite material freeze-dried powder is very easy to be re-dispersed in water, and the dispersed mixed solution can be stably stored for a period of time. FIG. 3 shows GO/C samples dispersed in water at a concentration of 2 mg/ml. The mixed liquor is in a relatively stable state in the initial 3 days after dispersion, no obvious precipitate is generated at the bottom of the sample bottle, and then the precipitate is generated at the bottom of the sample bottle in 15 days along with the lapse of time, and the supernatant liquid is gradually clear, but can still return to the initial dispersed state after shaking up. This is probably due to the uniform presence of micro and nano sized cellulose in the GO/C composite, which has a strong dispersibility in water, making the GO/C also easily dispersible in water, but due to the limited amount of these micro and nano sized cellulose, GO settles down due to sheet agglomeration once the solution is left to stand for a period of time.
The third concrete implementation mode:
a method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor comprises the following steps:
step a, preparing GO mixed acid liquid by using an improved Hummers method;
step b, extracting wood powder;
step c, pretreating lignocellulose by using the wood powder extracted in the step b;
step d, preparing the GO/cellulose composite material: and (c) adding the pretreated lignocellulose obtained in the step (c) into the GO mixed acid solution prepared in the step (a), heating for reaction, washing, filtering and dialyzing to be neutral, and freeze-drying or carrying out ultrasonic treatment on the obtained mixed solution and then freeze-drying to obtain the GO/cellulose composite material.
The fourth concrete implementation mode:
according to a third specific embodiment, the method for directly preparing the GO/cellulose composite material by mixing acid liquor by the Hummers method comprises the following steps:
step a1, weighing 55-60 ml of 98% concentrated sulfuric acid in a beaker, placing the beaker in an ice water bath, cooling the beaker to 2-5 ℃, and adding 2.5g of graphite powder and 1.25g of NaNO under the stirring condition3And 7.5g KMnO was added slowly4Keeping the reaction temperature below 10 ℃ and reacting for 90min to obtain a mixed solution for later use;
step a2, placing the mixed solution obtained in the step a1 in a warm water bath, controlling the reaction temperature to be 30-40 ℃ under the stirring condition, and reacting for 30-40 min to obtain a mixed solution for later use;
step a3, dropwise adding deionized water with the same volume as concentrated sulfuric acid under the stirring condition, controlling the reaction temperature to be 90-100 ℃, reacting for 15-25 min, and then adding H with the concentration of 30%2O2And adding the mixture into the mixed solution until no obvious bubbles are generated to obtain the GO mixed acid solution.
The fifth concrete implementation mode:
according to a third specific embodiment, the method for directly preparing the GO/cellulose composite material by mixing acid liquor by the Hummers method comprises the following steps:
step b1, mixing the raw materials in a volume ratio of 2: 1, weighing benzene and an absolute ethyl alcohol solution, and uniformly mixing for later use;
step b2, weighing a certain amount of wood powder, and drying the wood powder until the wood powder is absolutely dry for use;
b3, adding the mixed solution obtained in the step b1 into a 150ml soxhlet extractor, wherein the adding amount is 150-170 ml, then wrapping 3g of the wood flour prepared in the step b2 with filter paper, placing the wrapped wood flour into the bottom of the soxhlet extractor, controlling the reflux speed for 4 times/h, and extracting for 6h to obtain a product for later use;
and b4, drying the product prepared in the step b3 to obtain the extracted wood powder.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the heating temperature in the step b3 is 90 ℃.
The sixth specific implementation mode:
according to a third specific embodiment, the method for directly preparing the GO and cellulose composite material by mixing the acid solution by the Hummers method comprises the following steps:
step c1, adding 65ml of distilled water, 0.6g of sodium chlorite, 0.5ml of glacial acetic acid and 2g of the extracted wood flour prepared in the step b into a conical flask, uniformly mixing, treating in a water bath at 75 ℃ for 1 hour, then adding 0.6g of sodium chlorite and 0.5ml of glacial acetic acid, continuing to treat at 75 ℃ for 1 hour, and repeating the steps for 4-6 times to obtain a mixed solution for later use;
step c2, sucking and filtering the mixed solution obtained in the step c1, washing the mixed solution to be neutral by using distilled water, placing the obtained product into a 4% NaOH solution, and treating the product at 90 ℃ for 2 hours to obtain a mixed solution for later use;
and c3, sucking and filtering the mixed solution obtained in the step c2, washing the mixed solution with distilled water to be neutral, and drying the obtained product to obtain the pretreated lignocellulose.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, the temperature of the oven in the step c3 is 60 ℃.
The seventh embodiment:
according to a third specific embodiment, in the step d, 0.5g of the lignocellulose prepared in the step 3 is added into 20ml of the GO mixed acid solution prepared in the step 1, and the mixture is heated and reacted in a water bath at 45 ℃ for 2 hours under the condition of magnetic stirring.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution, after heating reaction, washing, filtering and dialyzing until the mixture is neutral, adding about 150ml of deionized water, stirring uniformly, standing for 12 hours, removing a supernatant, filtering a lower layer mixture by using a sand core funnel and a 0.45 mu m cellulose acetate microporous filter membrane, diluting substances on the filter membrane by using the deionized water, then putting the diluted substances into a dialysis bag, dialyzing until no precipitate is detected by using a barium chloride solution, and detecting the substances to be neutral by using a pH test paper.
In the method for directly preparing the GO/cellulose composite material by using the Hummers method mixed acid solution according to the embodiment, the ultrasonic treatment in the step d is ultrasonic power of 420W, and the ultrasonic time is 30 min.
The above examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention.
Claims (5)
1. A method for directly preparing GO/cellulose composite material by using Hummers method mixed acid liquor is characterized by comprising the following steps: the method comprises the following steps:
step a, preparing GO mixed acid liquid by using an improved Hummers method;
step b, extracting wood powder;
step c, pretreating lignocellulose, namely pretreating the wood powder extracted in the step b to obtain pretreated lignocellulose;
step d, preparing the GO/cellulose composite material: adding the pretreated lignocellulose obtained in the step c into the GO mixed acid solution prepared in the step a, heating for reaction, washing, filtering and dialyzing to be neutral, and freeze-drying or carrying out ultrasonic treatment on the obtained mixed solution and then freeze-drying to obtain a GO/cellulose composite material;
the step a comprises the following steps:
step a1, weighing 55-60 ml of 98% concentrated sulfuric acid in a beaker, placing the beaker in an ice water bath, cooling the beaker to 2-5 ℃, and adding 2.5g of graphite powder and 1.25g of NaNO under the stirring condition3And 7.5g KMnO was added slowly4Keeping the reaction temperature below 10 ℃ and reacting for 90min to obtain a mixed solution for later use;
step a2, placing the mixed solution obtained in the step a1 in a warm water bath, controlling the reaction temperature to be 30-40 ℃ under the stirring condition, and reacting for 30-40 min to obtain a mixed solution for later use;
step a3, dropwise adding deionized water with the same volume as concentrated sulfuric acid under the stirring condition, controlling the reaction temperature to be 90-100 ℃, reacting for 15-25 min, and then adding H with the concentration of 30%2O2Adding the mixture into the mixed solution until no obvious bubbles are generated to obtain GO mixed acid solution;
and d, adding 0.5g of lignocellulose prepared in the step c into 20ml of GO mixed acid liquor prepared in the step a, placing the mixture in a water bath at 45 ℃, and reacting for 2 hours under magnetic stirring.
2. The method for directly preparing GO/cellulose composite material by using Hummers method mixed acid solution as claimed in claim 1, wherein: the step c comprises the following steps:
step c1, adding 65ml of distilled water, 0.6g of sodium chlorite, 0.5ml of glacial acetic acid and 2g of the extracted wood flour prepared in the step b into a conical flask, uniformly mixing, treating in a water bath at 75 ℃ for 1 hour, then adding 0.6g of sodium chlorite and 0.5ml of glacial acetic acid, continuing to treat at 75 ℃ for 1 hour, and repeating the steps for 4-6 times to obtain a mixed solution for later use;
step c2, sucking and filtering the mixed solution obtained in the step c1, washing the mixed solution to be neutral by using distilled water, placing the obtained product into a 4% NaOH solution, and treating the product at 90 ℃ for 2 hours to obtain a mixed solution for later use;
and c3, sucking and filtering the mixed solution obtained in the step c2, washing the mixed solution with distilled water to be neutral, and drying the obtained product to obtain the pretreated lignocellulose.
3. The method for directly preparing GO/cellulose composite material by using Hummers method mixed acid solution as claimed in claim 2, wherein: the temperature of the oven of step c3 was 60 ℃.
4. The method for directly preparing GO/cellulose composite material by using Hummers method mixed acid solution as claimed in claim 1, wherein: and d, after the heating reaction is finished when the washing, filtering and dialysis are carried out until the neutrality is achieved, adding 150ml of deionized water, stirring uniformly, standing for 12h, removing the supernatant, filtering the lower-layer mixture by using a sand core funnel and a 0.45 mu m cellulose acetate microporous filter membrane, diluting substances on the filter membrane by using deionized water, then putting the substances into a dialysis bag for dialysis until no precipitate is detected by using a barium chloride solution, and detecting by using a pH test paper until the neutrality is achieved.
5. The method for directly preparing GO/cellulose composite material by using Hummers method mixed acid solution as claimed in claim 1, wherein: in the step d, the ultrasonic treatment is carried out with the ultrasonic power of 420W, the ultrasonic time is 30min, and the temperature is controlled at 20 ℃.
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