CN111056550B - Preparation method of graphene oxide/organic hollow silicon dioxide nanocomposite - Google Patents

Preparation method of graphene oxide/organic hollow silicon dioxide nanocomposite Download PDF

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CN111056550B
CN111056550B CN201911155003.1A CN201911155003A CN111056550B CN 111056550 B CN111056550 B CN 111056550B CN 201911155003 A CN201911155003 A CN 201911155003A CN 111056550 B CN111056550 B CN 111056550B
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graphene oxide
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CN111056550A (en
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陈连喜
方金金
吕博
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Wuhan University of Technology WUT
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Abstract

The invention discloses a preparation method of a graphene oxide/organic hollow silicon dioxide nano composite material. The method comprises the following steps: preparing graphene oxide; step two: preparing organic hollow silicon dioxide; preparing an organosilane composition with a core-shell structure by using organosilane with weak alkali resistance and organosilane with strong alkali resistance, and etching by using a NaOH solution to obtain organic hollow silicon dioxide; step three: preparing a graphene oxide/organic hollow silica nanocomposite; and (3) enabling the organic hollow silica to carry positive charges, and then combining with the graphene oxide carrying negative charges to obtain the graphene oxide/organic hollow silica nanocomposite. The invention has the advantage of excellent adsorption performance.

Description

Preparation method of graphene oxide/organic hollow silicon dioxide nanocomposite
Technical Field
The invention relates to the field of nano composite materials, in particular to a preparation method of a graphene oxide/organic hollow silicon dioxide nano composite material.
Background
Since 2004, geom et al obtained graphene stably existing by using a mechanical exfoliation method, graphene has attracted great interest to researchers because of its excellent electrical properties, excellent thermal conductivity, large specific surface area, high young's modulus and breaking strength.
As a graphene derivative, graphene oxide not only has the large specific surface area, excellent thermal conductivity and excellent mechanical properties of graphene, but also contains a large number of oxygen-containing groups after deep oxidation, and the oxygen-containing groups not only provide a large number of active sites for graphene oxide, but also enable the graphene oxide to have good hydrophilic properties, and can be easily dispersed in water and other polar solvents by ultrasound. However, graphene oxide has a disadvantage of being easily agglomerated, and thus it is necessary to modify graphene oxide or to compound graphene oxide with other materials.
The silicon dioxide has the advantages of low density, low toxicity, good biocompatibility, excellent chemical and thermal stability and the like. Through the compounding of the graphene oxide and the silicon dioxide material, the agglomeration of the graphene oxide can be inhibited to a great extent, and the advantages of the graphene oxide and the silicon dioxide material are complementary. However, in the synthesis of graphene oxide and silica composite materials, the silicon hydroxyl group on the surface of inorganic silica is not enough to meet the requirements of practical application, and most of inorganic silica is solid silica spheres without any hollow or mesoporous structure, so that the preparation of silica with organic groups and special structures can improve the performance of the composite to meet the requirements of practical application, especially adsorption application.
Therefore, there is a need to develop a graphene oxide and silica composite material having better adsorption performance.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene oxide/organic hollow silica nanocomposite; according to the method, the ectopic charge interaction is adopted (namely, hydrochloric acid is dripped to enable the organic hollow silica to be positively charged and then to be subjected to ectopic compounding with the negatively charged graphene oxide), so that the problem that the graphene oxide is difficult to separate in water is solved, and the graphene oxide is prevented from agglomerating; in addition, due to the high surface area of the graphene oxide and the organic hollow silica, the composite material has excellent adsorption performance after the graphene oxide and the organic hollow silica are combined.
In order to achieve the purpose, the technical scheme of the invention is as follows: the preparation method of the graphene oxide/organic hollow silicon dioxide nano composite material is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
the method comprises the following steps: preparing graphene oxide;
step two: preparing organic hollow silica;
preparing an organosilane composition with a core-shell structure by using organosilane with weak alkali resistance and organosilane with strong alkali resistance, and etching by using a NaOH solution to obtain organic hollow silicon dioxide;
step three: preparing a graphene oxide/organic hollow silica nanocomposite;
and (3) enabling the organic hollow silica to carry positive charges, and then combining with the graphene oxide carrying negative charges to obtain the graphene oxide/organic hollow silica nanocomposite.
In the above technical solution, in the first step, the preparation of graphene oxide comprises the following steps:
s11: adding 3-9 g of graphite powder, 1-3 g of sodium nitrate and 100-150 mL of concentrated sulfuric acid into a three-neck flask, adding into the mixed system, controlling the temperature of the system to be lower than 5 ℃, and reacting for 2-3 h under the condition; obtaining a first system;
s12: adding 18-30 g of potassium permanganate into the first system for multiple times within 1 hour, and maintaining the temperature of the first system to be not more than 10 ℃ through an ice water bath;
then mechanically stirring for 1-2 h, then converting the ice water bath into a warm water bath, maintaining the temperature of the first system at about 35 ℃, and mechanically stirring for 2-4 h; obtaining a second system;
s13: slowly adding 200-300 mL of deionized water into the second system for rapid stirring, and controlling the temperature of the second system not to exceed 90 ℃; stirring for 15-30 min, slowly adding 100-200 mL of hydrogen peroxide into the second system until the system turns to bright yellow; obtaining a first product;
s14: washing the first product with 1.45mol/L diluted hydrochloric acid for several times until no precipitate is generated after the first product is added with barium chloride;
washing with water for multiple times until no precipitate is generated when silver nitrate is added into the first product;
and finally, freeze-drying the first product to obtain the graphene oxide.
In the technical scheme, in S11, graphite powder and sodium nitrate are added into a three-neck flask, and the amount of the graphite powder and the amount of the sodium nitrate are respectively 6g and 3g; the concentrated sulfuric acid is 150mL; controlling the temperature of the system to be lower than 5 ℃, and reacting for 3 hours in the state;
in S12, 24g of potassium permanganate is added;
in S13, 270mL of deionized water was used.
In the above technical solution, in the second step, the preparation of the organic hollow silica comprises the following steps:
s21: adding 0.3-0.4 mL of Vinyl Triethoxysilane (VTES) or 2-Cyanopropyltriethoxysilane (CTES) into a solution containing 40-50 mL of deionized water and 5-10 mL of anhydrous ethanol, and reacting at 35 ℃ for 2-3 h; obtaining a third system;
s22: adding 0.5-1.0 mL of ammonia water into the third system, and reacting for 6-10 h; obtaining a fourth system;
s23: adding 0.4-0.5 mL of 3-thiocyanatopropyltriethoxysilane (TCPTES) into the fourth system, and continuing stirring for 6-8 h; obtaining a second product;
s24: carrying out solid-liquid separation on the second product to obtain a third product;
washing the third product with deionized water and ethanol respectively, and drying the third product in a drying oven at the temperature of 70 ℃ to obtain 2.0-2.5 mg of organic functionalized silicon dioxide with a core-shell structure;
s25: adding the organic functionalized silicon dioxide with the core-shell structure prepared in the S24 into a sodium hydroxide solution with the concentration of 0.5-1.0 mol/L, performing ultrasonic treatment for 5-10 min to disperse the organic functionalized silicon dioxide with the core-shell structure, and reacting at 60 ℃ for 10-12 h; obtaining a fourth product;
s26: and finally, centrifugally separating, washing the fourth product with deionized water and ethanol for multiple times, and drying the fourth product in a drying box at the temperature of 70 ℃ to obtain 0.7-1.2 mg of organic hollow silica.
In the above technical solution, in the second step, the organic hollow silica is at least thiocyano-functionalized hollow silica or mercapto-functionalized hollow silica or ureido-functionalized hollow silica or amino-functionalized hollow silica.
In the above technical solution, in step S21, 0.3mL of Vinyltriethoxysilane (VTES) or 2-Cyanopropyltriethoxysilane (CTES) is added;
in step S23, 3-thiocyanatopropyltriethoxysilane was added in an amount of 0.4mL.
In the above technical scheme, in the third step, the graphene oxide/organic hollow silica nanocomposite is prepared, which includes the following steps:
s31: dispersing 30-60 mg of graphene oxide prepared in the first step in deionized water; then carrying out ultrasonic treatment for 2-3 h under the ultrasonic power of 180-200W; obtaining a first suspension;
s32: dispersing 60-120 mg of the organic hollow silica prepared in the second step in deionized water; then carrying out ultrasonic treatment for 5-10 min under the ultrasonic power of 180-200W; obtaining a second suspension;
then adding concentrated hydrochloric acid with the volume of 0.2-0.4 mL into the second suspension; obtaining a third suspension;
s33: and finally, mixing the first suspension and the third suspension, mechanically stirring for 6-10 hours at 70 ℃, then performing centrifugal separation, and drying the solid to obtain the graphene oxide/organic hollow silica nanocomposite.
In the above technical scheme, in the third step, the graphene oxide/organic hollow silica nanocomposite is at least graphene oxide/thiocyano functionalized hollow silica nanocomposite (GO/NCS-HSNs) or graphene oxide/mercapto functionalized hollow silica nanocomposite (GO/HS-HSNs), or graphene oxide/ureido functionalized hollow silica or graphene oxide/amino functionalized hollow silica.
In the above technical solution, in step S32, 120mg of organic hollow silica is dispersed in deionized water;
in step S32, concentrated hydrochloric acid was added in a volume of 0.4mL.
The invention has the following advantages:
(1) According to the invention, by adopting a strategy of ectopic charge interaction, organic hollow silica is charged with positive electricity by dripping hydrochloric acid, and then ectopic recombination is carried out on the organic hollow silica and graphene oxide with negative electricity, so as to obtain a graphene oxide/organic hollow silica nanocomposite; the problem that graphene oxide is difficult to separate from a polar solvent (namely difficult to separate in water) is solved, and the agglomeration of the graphene oxide is prevented; in addition, due to the high surface areas of the graphene oxide and the organic hollow silica, the composite material has excellent adsorption performance after the graphene oxide and the organic hollow silica are combined;
(2) The graphene oxide/organic hollow silicon dioxide nano composite material prepared by the method is simple and convenient to operate and is green and environment-friendly;
(3) The method can be used for compounding inorganic silicon dioxide and graphene oxide, and is also a general method for compounding organic hybrid silicon dioxide and graphene oxide;
(4) The adsorption effect is improved through the compound preparation and the synergistic effect of all the components; the invention has excellent adsorption performance; the invention researches the removal effect of the graphene oxide/organic hollow silica nano composite material on methylene blue, and finds that the adsorption capacity of the graphene oxide/organic hollow silica nano composite material on the methylene blue is obviously improved compared with that of the graphene oxide/organic silica nano material and a single organic hollow silica nano particle;
(5) According to the invention, the silicon dioxide with organic groups and hollow structures is prepared, and the performance of the compound can be improved after the silicon dioxide is compounded with graphene oxide so as to meet the requirements of practical application, especially on adsorption;
(6) The invention has better adsorption effect on methylene blue and other substances (such as heavy metals, organic pollutants and the like in water).
The graphene oxide/organic hollow silicon dioxide nano composite material can be various organic functional groups as long as the alkali resistance of two types of organic silane is different; different organic hollow silica can be obtained by differential etching according to organic functional groups, then acid is added to enable the organic hollow silica to be positively charged, and finally the organic hollow silica is compounded with graphene oxide with negative charges to obtain various GO/organic hollow silica nano composite materials.
The invention creatively changes the charge property of the surface of the organic hollow silica by adding hydrochloric acid, so that the silica originally charged with negative electricity is charged with positive electricity, and can be better compounded with the graphene oxide charged with negative electricity through the interaction of ectopic charges; the method is simple to operate and has universality; the graphene oxide/organic hollow silica composite material is creatively prepared, and the graphene oxide/organic hollow silica composite material is used for adsorbing methylene blue for the first time, so that the adsorption effect is remarkably improved compared with that of pure organic hollow silica and GO/organic silica.
Drawings
Fig. 1-a is a micron-scale SEM image of prior art graphene oxide.
FIG. 1-b is a nanometer-scale SEM image of a single prior art thiocyano-functionalized hollow silica.
FIG. 1-c is a nanometer-scale SEM image of a prior art single mercapto-functionalized hollow silica.
Fig. 1-d is a nano-scale SEM image of the graphene oxide/thiocyano functionalized hollow silica nanocomposite of the present invention.
Fig. 1-e is a nano-scale SEM image of graphene oxide/thiol functionalized hollow silica nanocomposites of the present invention.
Fig. 1-f are prior art SEM images of a mixture of thiocyano functionalized hollow silica and graphene oxide without addition of acid.
Fig. 2-a is a TEM image of a prior art graphene oxide/thiocyano functionalized silica composite at the nanometer scale.
Fig. 2-b is a TEM image of the graphene oxide/thiocyano functionalized hollow silica composite of the present invention at a nanometer scale.
Fig. 2-c is a micron-scale TEM image of the graphene oxide/thiol functionalized hollow silica composite of the present invention.
FIG. 3-a is a graph showing the specific surface area and pore size distribution of a single thiocyano-functionalized hollow silica of the present invention.
Fig. 3-b is a specific surface area and pore size distribution diagram of the graphene oxide/thiocyano functionalized hollow silica nanocomposite of the present invention.
FIG. 3-c is a graph showing the specific surface area and pore size distribution of a single mercapto-functionalized hollow silica of the present invention.
Fig. 3-d is a specific surface area and pore size distribution diagram of the graphene oxide/thiol functionalized hollow silica nanocomposite of the present invention.
Figure 4 is a XRD chart of the present invention.
FIG. 5-a is an XPS full scan spectrum of a graphene oxide/thiocyano functionalized hollow silica nanocomposite of the present invention.
FIG. 5-b is an XPS full scan spectrum of a graphene oxide/thiol functionalized hollow silica nanocomposite of the present invention.
FIG. 5-c is an XPS single scan spectrum of graphene oxide/thiocyano functionalized hollow silica nanocomposite Si2p of the present invention.
FIG. 5-d is an XPS single scan spectrum of graphene oxide/thiol functionalized hollow silica nanocomposite Si2p of the present invention.
Fig. 6-a is a graph showing the adsorption of methylene blue by the graphene oxide/thiocyano functionalized hollow silica nanocomposite according to the present invention.
Fig. 6-b is an adsorption curve diagram of the graphene oxide/thiol-functionalized hollow silica nanocomposite according to the present invention on methylene blue.
FIG. 7 is a process flow diagram of the present invention.
Description of the drawings: in FIG. 1-a, it can be seen that the GO surface is very smooth and its agglomeration is also evident. FIGS. 1-b and 1-c show pure organic hollow silica with no signs of wrinkles on the surface; as clearly seen in FIGS. 1-d and 1-e, after GO and OHSN are combined, the GO film tightly wraps the silica surface. However, FIG. 1-f is significantly different from FIGS. 1-d and 1-e, indicating that NCS-HSNs are deposited on the surface of GO when they are not treated with hydrochloric acid; the main reason for this is that NCS-HSNs and GO are both negatively charged and easily repel each other; thus, SEM analysis successfully demonstrated that OHSN could be better encapsulated by GO after acid treatment; at the same time, it has also been demonstrated that ectopic charge interaction strategies can be used to prepare GO/OHSNs composites.
In FIG. 1-a, 1um on the picture indicates the scale in micrometer units; i.e. the graphene oxide therein has a size of 1um.
In FIG. 1-a, 100nm on the picture represents the scale in nanometer units; i.e. wherein the size of the single thiocyano-functionalized hollow silica is 100nm.
In FIG. 1-c, 200nm on the picture indicates the scale as nanometer units; i.e. wherein the size of the single mercapto functionalized hollow silica is 200nm.
In FIG. 1-d, 100nm on the picture represents the scale in nanometer units; namely, the size of the graphene oxide/thiocyano functionalized hollow silica nanocomposite is 100nm.
In FIG. 1-e, 100nm on the picture represents the scale in nanometer units; namely, the size of the graphene oxide/sulfydryl functionalized hollow silica nano-composite is 100nm.
In FIG. 1-f, 2um on the picture indicates the scale is in micrometer units; i.e. a mixture of hollow silica functionalized with thiocyano groups without addition of acid and graphene oxide therein, has a size of 2um.
In FIG. 2-a, 100nm on the picture represents the scale in nanometer units; i.e. wherein the graphene oxide/thiocyano functionalized silica composite has a size of 100nm.
In FIG. 2-b, 100nm on the picture indicates the scale as nanometer units; namely, the size of the graphene oxide/thiocyano functionalized hollow silica composite is 100nm.
In FIG. 2-c, 0.2um on the picture indicates the scale in micrometer units; i.e. wherein the graphene oxide/thiol functionalized hollow silica composite is 0.2um in size.
As can be seen from fig. 2-a, the organic silica having a core-shell structure is solid inside before being etched by the sodium hydroxide solution; while GO/HS-HSNs in figures 2-b and 2-c), after GO and OHSN are compounded, the hollow structure of OHSN is clear and obvious; in addition, it is also clear that the surface of NCS-HSNs and HS-HSNs are covered by a clear film, indicating that the surface of OHSNs is covered by a GO film by the ectopic charge interaction strategy.
From FIGS. 3-a and 3-b, it can be seen that the specific surface areas of NCS-HSN and GO/NCS-HSNs are 16.96m 2 G and 79.38m 2 (iv) g; notably, after the incorporation of GO, the surface area of GO/NCS-HSNs composites increased dramatically; this demonstrates that the strategy for making GO/OHSNs composites by ex-situ charge interaction methods is successful; as can be seen from FIGS. 3-c and 3-d, the trends of the changes in the specific surface areas for HS-HSN and GO/HS-HSN are the same as those for NCS-HSN and GO/NCS-HSN.
In fig. 4, a is an XRD profile of graphene oxide, which is the lower-lying profile in fig. 4; b is the XRD profile of the graphene oxide/thiocyano functionalized hollow silica nanocomposite, which is the curve located in the middle in fig. 4; c is the XRD profile of the graphene oxide/mercapto functionalized hollow silica nanocomposite, which is the upper curve in fig. 4;
a strong diffraction peak at 2 θ =10 ° in the a-curve in fig. 4, which is due to diffraction of the (002) plane of graphene oxide, indicating that graphene oxide has a highly ordered structure, with a weak broad diffraction peak at 20.2 ° due to the short angular steps in the laminated graphene swatch; meanwhile, in the b curve and the c curve in fig. 4, the diffraction peak intensity of the GO/OHSNs composite at 2 θ =10 ° weakens or even disappears, which is to say that the graphene oxide stacking disappears or is a high disorder in which the stacking thereof exists, because both the acid-treated organic hollow silica and the graphene oxide have electrostatic attraction to each other, which is stronger than the hydrogen bond and van der waals force between the graphene oxide sheet layers, thus causing the graphene oxide to accumulate a high disorder by itself after coating the organic hollow silica.
From FIGS. 5-a and 5-b, it can be seen that the GO/NCS-HSNs and GO/HS-HSNs composites exhibit the presence of N, S, O, C and Si elements; meanwhile, the single-scan spectra of high resolution in Si2p are shown in FIGS. 5-c and 5-d; it can be clearly seen that two peaks with binding energies of 101eV and 103eV, respectively, appear, corresponding to the Gaussian peaks of Si-C or Si-S and Si-O-Si, respectively; this indicates that graphene oxide is physically bound to OHSNs; if graphene oxide and OHSNs are bonded by chemical bonds, the Si element will have three different chemical states; thus, XPS results demonstrate that graphene oxide does not form new chemical bonds when bound to OHSNs.
From fig. 6-a and 6-b, it can be seen that the adsorption capacity of the graphene oxide/organic hollow silica nanocomposite for methylene blue rapidly increases within 60 minutes initially, then the adsorption rate of the composite for methylene blue begins to slow down after adsorption sites on the surface of the composite are gradually occupied, and finally the equilibrium is reached within 180 minutes; moreover, after graphene oxide and organic hollow silica are compounded, the adsorption capacity of the compound to methylene blue is obviously higher than that of a single organic hollow silica nano particle and graphene oxide/organic silica nano compound; the result shows that the graphene oxide/organic hollow silica nanocomposite prepared by the invention has a promotion effect on the adsorption of methylene blue as an adsorbent.
In fig. 7, the one-pot method is prior art.
Detailed Description
The embodiments of the present invention will be described in detail with reference to the drawings, but the present invention is not limited to these embodiments. While the advantages of the invention will be clear and readily understood by the description.
With reference to FIG. 1: the preparation method of the graphene oxide/organic hollow silicon dioxide nano composite material comprises the following steps,
the method comprises the following steps: preparing graphene oxide;
step two: preparing organic hollow silicon dioxide;
preparing an organosilane composition with a core-shell structure by using organosilane with weak alkali resistance and organosilane with strong alkali resistance (the alkali resistance of the organosilane with strong alkali resistance is relative to the organosilane with weak alkali resistance, namely the alkali resistance of the organosilane with strong alkali resistance is greater than that of the organosilane with weak alkali resistance), and etching the organosilane with weak alkali resistance by using a NaOH solution to obtain the organic hollow silica with strong alkali resistance;
step three: preparing a graphene oxide/organic hollow silica nanocomposite;
and (3) enabling the organic hollow silica to carry positive charges, and then combining with the graphene oxide carrying negative charges to obtain the graphene oxide/organic hollow silica nanocomposite.
Further, in the step one, preparing graphene oxide comprises the following steps:
s11: adding 3-9 g of graphite powder, 1-3 g of sodium nitrate and 100-150 mL of concentrated sulfuric acid into a three-neck flask, adding into the mixed system, and reacting for 2-3 h under the condition of normal pressure and the temperature of the system controlled to be lower than 5 ℃; obtaining a first system;
s12: adding 18-30 g of potassium permanganate into the first system for multiple times within 1 hour, and maintaining the temperature of the first system to be not more than 10 ℃ through an ice water bath;
then mechanically stirring for 1-2 h, then converting the ice water bath into a warm water bath, maintaining the temperature of the first system at about 35 ℃, and mechanically stirring for 2-4 h; obtaining a second system;
s13: slowly adding 200-300 mL of deionized water into the second system for rapid stirring, and controlling the temperature of the second system not to exceed 90 ℃; stirring for 15-30 min, slowly adding 100-200 mL of hydrogen peroxide into the second system until the system turns to bright yellow; obtaining a first product;
s14: washing the first product with 1.45mol/L diluted hydrochloric acid for several times until no precipitate is generated after the first product is added with barium chloride;
washing with water for eight times until no precipitate is generated when silver nitrate is added into the first product;
and finally, freeze-drying the first product to obtain the graphene oxide.
Further, in S11, graphite powder and sodium nitrate are added into a three-neck flask, and the amount of the graphite powder and the amount of the sodium nitrate are respectively 6g and 3g; the concentrated sulfuric acid is 150mL; controlling the temperature of the system to be lower than 5 ℃, and reacting for 3 hours in the state;
in S12, 24g of potassium permanganate is added;
in S13, 270mL of deionized water was used.
The preparation of the graphene oxide is prior art.
Further, in the second step, the organic hollow silica is prepared, which comprises the following steps:
s21: adding 0.3-0.4 mL of VTES or CTES into a solution containing 40-50 mL of deionized water and 5-10 mL of absolute ethyl alcohol, and reacting at 35 ℃ for 2-3 h under normal pressure; obtaining a third system;
s22: adding 0.5-1.0 mL of ammonia water into the third system, and reacting for 6-10 h; obtaining a fourth system;
s23: adding 0.4-0.5 mL of TCPTES (the TCPTES can be replaced by silica with other organic functional groups, and the silica with other organic functional groups meets the alkali resistance which is stronger than that of Vinyltriethoxysilane (VTES) or 2-Cyanopropyltriethoxysilane (CTES)) into the fourth system, and continuously stirring for 6-8 h; obtaining a second product;
s24: carrying out solid-liquid separation on the second product to obtain a third product;
washing the third product with deionized water and ethanol respectively, and drying the third product in a drying oven at the temperature of 70 ℃ to obtain 2.0-2.5 mg of organic functionalized silicon dioxide with a core-shell structure;
s25: adding the organic functionalized silicon dioxide with the core-shell structure prepared in the S24 into a sodium hydroxide solution with the concentration of 0.5-1.0 mol/L (namely, the sodium hydroxide solution is adopted to etch the organic functionalized silicon dioxide with the core-shell structure, and VTES or CTES with weak alkali resistance is etched), and carrying out ultrasonic treatment for 5-10 min to disperse the organic functionalized silicon dioxide with the core-shell structure, and reacting for 10-12 h at 60 ℃ under the normal pressure condition; obtaining a fourth product;
s26: and finally, centrifugally separating, washing the fourth product for multiple times by using deionized water and ethanol respectively, and then putting the fourth product into a drying oven at the temperature of 70 ℃ for drying to obtain 0.7-1.2 mg of organic hollow silica with strong alkali resistance.
Further, in the second step, the organic hollow silica is at least NCS-HSNs or HS-HSNs; the hollow organic silica may also be hollow silica with other organic functional groups (such as mercapto-functionalized hollow silica, ureido-functionalized hollow silica, amino-functionalized hollow silica, etc.) according to the requirement.
The preparation method of the invention has two functions: (1) The graphene oxide/graphene oxide composite material is compounded with GO (graphene oxide), so that the problem that GO is difficult to separate in water can be solved; (2) Because the hollow silicon dioxide of thiocyanogen group and hollow silicon dioxide of sulfydryl group are hollow structures, the specific surface area of the hollow silicon dioxide is increased compared with that of the solid silicon dioxide, and the specific surface area of the compound can be increased, so that the adsorption performance is improved.
The invention creatively provides the difference etching of organic functional groups to prepare various organic hollow silicon dioxide, and only two organosilanes with different alkali resistances are selected; namely, two organosilanes with different alkali resistances are selected to prepare silicon dioxide with a core-shell structure, and then according to the different alkali resistances of each organosilane, organosilane with relatively weak alkali resistance is etched away by NaOH, so that hollow organic silicon dioxide is obtained; at present, it is common to employ VTES and CTES as the core, mercapto and thiocyano groups and also urea groups as the shell; the invention can be applied to the preparation of hollow silica with various organic functional groups.
Further, in step S21, VTES or CTES was added at 0.3mL;
in step S23, 3-thiocyanatopropyltriethoxysilane or other organofunctional silica was added in an amount of 0.4mL.
Further, in step three, a graphene oxide/organic hollow silica nanocomposite is prepared, which comprises the following steps:
s31: dispersing 30-60 mg of graphene oxide prepared in the first step in deionized water; then carrying out ultrasonic treatment for 2-3 h under the ultrasonic power of 180-200W; obtaining a first suspension;
s32: dispersing 60-120 mg of the organic hollow silica prepared in the second step in deionized water; then carrying out ultrasonic treatment for 5-10 min under the ultrasonic power of 180-200W; obtaining a second suspension;
then adding concentrated hydrochloric acid with the volume of 0.2-0.4 mL into the second suspension; obtaining a third suspension;
s33: and finally, mixing the first suspension and the third suspension, mechanically stirring for 6-10 hours at 70 ℃ under the normal pressure condition, then carrying out centrifugal separation, taking the solid and drying to obtain the graphene oxide/organic hollow silica nanocomposite.
According to the method, hydrochloric acid is dropwise added in step S32, so that silica originally with negative electricity is positively charged, and graphene oxide with negative electricity can be better compounded with the silica through the interaction of ectopic charges, and the GO/organic hollow silica nanocomposite with excellent adsorption performance is creatively prepared.
Further, in step three, the graphene oxide/organic hollow silica nanocomposite is at least GO/NCS-HSNs nanocomposite or graphene oxide/mercapto functionalized hollow silica nanocomposite (GO/HS-HSNs).
According to the invention, the graphene oxide is adopted to wrap the organic hollow silica, so that the specific surface area of the composite is increased, and the specific surface area of the composite is increased, thereby improving the adsorption performance; and simultaneously, the problem that the graphene oxide is difficult to separate in water is solved.
Further, in step S32, 120mg of organic hollow silica is dispersed in deionized water; in step S32, concentrated hydrochloric acid was added in a volume of 0.4mL.
The graphene oxide/organic hollow silica nanocomposite prepared by the method has universality, and can be used for preparing silica with different organic functional groups, and the silica with different organic functional groups is compounded with graphene oxide, so that different types of graphene oxide/organic hollow silica nanocomposites are obtained; the invention is not limited to the preparation of only one compound; the invention can prepare various compounds with similar adsorption functions;
the invention aims to select and prepare GO/NCS-HSNs and GO/HS-HSNs, so that two organic functional groups, namely thiocyano hollow silica and mercapto hollow silica, are relatively common, and the cost is lower compared with other organic silica.
Examples
The invention is explained in detail by taking the embodiment of preparing NCS-HSNs by the method as an example, and has the same guiding function for preparing other graphene oxide/organic hollow silicon dioxide nano composite materials.
Example 1
The product prepared in this example was GO/NCS-HSNs;
the specific steps for preparing NCS-HSNs are as follows:
the method comprises the following steps: preparing graphene oxide;
adding graphite powder and sodium nitrate into a three-neck flask, wherein the amount of the graphite powder and the sodium nitrate is 6g and 3g respectively, further adding 150mL of concentrated sulfuric acid into the mixed system, and controlling the temperature of the system to be lower than 5 ℃; after reacting for 2 hours in this state, 24g of potassium permanganate is added into the system in 4g each time for 6 times in 1 hour, and the temperature of the system is maintained to be not more than 10 ℃ through an ice water bath; then mechanically stirring for 1h, converting the ice-water bath into a warm water bath, maintaining the temperature of the system at about 35 ℃, and mechanically stirring for 2h; then slowly adding 270mL of deionized water into the system for rapid stirring, and controlling the temperature of the system not to exceed 90 ℃; after stirring for 15min, slowly adding hydrogen peroxide into the reaction system in order to remove unreacted potassium permanganate until the system turns into bright yellow; then washing the product with 1.45mol/L diluted hydrochloric acid for several times until no precipitate is generated after barium chloride is added; washing with water for several times until no precipitate is generated after adding silver nitrate; finally, drying the product in a drying oven at 60 ℃ to obtain uncarboxylated graphene oxide, then ultrasonically dispersing 0.75g of uncarboxylated graphene oxide in 300mL of deionized water, then adding 50mL of hydrogen bromide at room temperature, and mechanically stirring for 12h; adding 15g of oxalic acid into the reaction system, and continuing to react for 4 hours; finally, the product was washed several times with water and then dried in a drying oven at 50 ℃.
Step two: preparing organic hollow silica;
5mL of ethanol and 45mL of water, 0.5mL of an aqueous ammonia solution were added to a 100mL three-necked flask, and stirred at 35 ℃ for 1 hour. Then 0.3mL of Vinyltriethoxysilane (VTES) or CTES was added to the above system during vigorous stirring. The above mixed solution was further stirred at 35 ℃ for 6 hours to obtain a white colloidal suspension. Subsequently, 0.4mL of 3-thiocyanatopropyltriethoxysilane (TCPTES) was added and after stirring at 35 ℃ for 6h, the collected white product was centrifuged and washed 3 times with deionized water and ethanol (95%), respectively. Finally, drying the synthesized sample at 60 ℃ for 12h to obtain the organic functionalized silicon dioxide (CH) with the core-shell structure 2 ＝CH-SNs@NCS-SNs)。CH 2 Process for producing = CH-SNs @ HS-SNs and CH as described above 2 The preparation steps of = CH-SNs @ NCS-SNs are the same.
Step three: preparing a graphene oxide/organic hollow silica nanocomposite;
subjecting the obtained CH 2 And (2) ultrasonically dispersing the = CH-SNs @ NCS-SNs nano particles in 0.05M NaOH, stirring for 12 hours at 60 ℃, finally performing centrifugal separation, and washing with ethanol and deionized water for three times respectively to obtain NCS-HSNs. The preparation method of HS-HSNs is the same as that of NCS-HSNs.
Ultrasonically dispersing graphene oxide with the mass of 60mg in deionized water with the volume of 120mL, and then dispersing organic hollow silicon dioxide with the mass of 120mg in anhydrous ethanol with the volume of 60 mL; then adding concentrated hydrochloric acid with the volume of 0.4mL into the suspension of the organic hybrid silicon dioxide; and finally, mixing the two suspensions, mechanically stirring for 6 hours at 70 ℃, separating a product from the solution, washing the product once with deionized water, washing the product once with ethanol, and drying the product in a drying oven at 70 ℃ to obtain the graphene oxide/thiocyano functionalized hollow silica nano composite (GO/NCS-HSNs).
And (4) conclusion: the NCS-HSNs prepared by the embodiment have excellent adsorption performance; simple operation and environmental protection.
Example 2
The product prepared in this example was GO/HS-HSNs;
the preparation method is the same as that of example 1; the difference lies in that: the product prepared in this example is a graphene oxide/mercapto functionalized hollow silica nanocomposite (GO/HS-HSNs); the prepared organic hollow silica is hollow silica with a functionalized thiocyano group.
And (4) conclusion: the GO/HS-HSNs prepared by the embodiment have excellent adsorption performance; simple operation and environmental protection.
Example 3
The product prepared in this example was GO/NCS-HSNs;
the preparation method is the same as example 1; the difference lies in that: in the first step, when graphene oxide is prepared, in S11, 6g of graphite powder, 2g of sodium nitrate and 120mL of concentrated sulfuric acid are added, the temperature of a system is controlled to be lower than 5 ℃, and the reaction is carried out for 3 hours in the state;
in S12, 25g of potassium permanganate is added;
in S13, 250mL of deionized water is added; stirring for 25min; the added hydrogen peroxide is 150mL;
in the second step, when preparing the organic hollow silica, 0.35mL of Vinyltriethoxysilane (VTES) is added to a solution containing 46mL of deionized water and 8mL of anhydrous ethanol in S21, and reacted at 35 ℃ for 3 hours;
in S22, 0.8mL of ammonia water is added into the system to react for 8h;
in S23, 0.5mL of 3-thiocyanatopropyltriethoxysilane (TCPTES) is added into the mixed system, and the mixture is stirred for 7 hours;
in S24, 2.3mg of organofunctionalized silica (CH) of core-shell structure are obtained 2 ＝CH-SNs@NCS-SNs)；
In S25, the concentration of the sodium hydroxide solution is 0.7mol/L; reacting for 11h at 60 ℃;
in S26, 1.0mg of thiocyano-functionalized hollow silica (NCS-HSNs) were obtained;
in the third step, when the graphene oxide/organic hollow silica nanocomposite is prepared, in S32, 100mg of thiocyanato-functionalized hollow silica is dispersed in deionized water; the volume of the added concentrated hydrochloric acid was 0.2mL.
And (4) conclusion: the GO/NCS-HSNs prepared by the embodiment have excellent adsorption performance; simple operation and environmental protection.
Example 4
The product prepared in this example was GO/NCS-HSNs;
the preparation method is the same as that of example 1; the difference lies in that: in the first step, when graphene oxide is prepared, 9g of graphite powder, 3g of sodium nitrate and 150mL of concentrated sulfuric acid are added in S11, the temperature of a system is controlled to be lower than 5 ℃, and the reaction is carried out for 3 hours in the state;
in S12, 30g of potassium permanganate is added;
in S13, 300mL of deionized water is added; stirring for 30min; adding 200mL of hydrogen peroxide;
in the second step, in preparing the organic hollow silica, 0.4mL of Vinyltriethoxysilane (VTES) is added to a solution containing 50mL of deionized water and 10mL of anhydrous ethanol in S21, and reacted at 35 ℃ for 3 hours;
in S22, 1.0mL of ammonia water is added into the system and reacts for 10h;
in S23, 0.5mL of 3-thiocyanatopropyltriethoxysilane (TCPTES) is added into the mixed system, and the mixture is stirred for 8 hours;
in S24, 2.5mg of organofunctionalized silica (CH) of core-shell structure are obtained 2 ＝CH-SNs@NCS-SNs)；
In S25, the concentration of the sodium hydroxide solution is 1.0mol/L; reacting for 12h at 60 ℃;
in S26, 1.2mg of thiocyano-functionalized hollow silica (NCS-HSNs) were obtained;
in the third step, when the graphene oxide/organic hollow silica nanocomposite is prepared, in S32, 120mg of thiocyanato-functionalized hollow silica is dispersed in deionized water; the volume of concentrated hydrochloric acid added was 0.4mL.
And (4) conclusion: the GO/NCS-HSNs prepared by the embodiment have excellent adsorption performance; simple operation and environmental protection.
Example 5
The product prepared in this example was GO/NCS-HSNs;
the preparation method is the same as that of example 1; the difference lies in that: in the first step, when graphene oxide is prepared, in S11, 3g of graphite powder, 1g of sodium nitrate and 100mL of concentrated sulfuric acid are added, the temperature of a system is controlled to be lower than 5 ℃, and the reaction is carried out for 2 hours in the state;
in S12, 18g of potassium permanganate is added;
in S13, 200mL of deionized water is added; stirring for 15min; the added hydrogen peroxide is 100mL;
in the second step, when preparing the organic hollow silica, 0.3mL of Vinyltriethoxysilane (VTES) is added to a solution containing 40mL of deionized water and 5mL of anhydrous ethanol in S21, and reacted at 35 ℃ for 2h;
in S22, adding 0.5mL of ammonia water into the system, and reacting for 6h;
in S23, 0.4mL of 3-thiocyanatopropyltriethoxysilane (TCPTES) is added into the mixed system, and stirring is continued for 6 hours;
in S24, 2.0mg of organofunctionalized silica (CH) of core-shell structure are obtained 2 ＝CH-SNs@NCS-SNs)；
In S25, the concentration of the sodium hydroxide solution is 0.5mol/L; reacting for 10 hours at 60 ℃;
in S26, 0.7mg of thiocyano-functionalized hollow silica (NCS-HSNs) are obtained;
in the third step, when the graphene oxide/organic hollow silica nanocomposite is prepared, in S32, 60mg of thiocyanato-functionalized hollow silica is dispersed in deionized water; the volume of concentrated hydrochloric acid added was 0.2mL.
And (4) conclusion: the GO/NCS-HSNs prepared by the embodiment have excellent adsorption performance; simple operation and environmental protection.
And (3) verification:
the method for testing the adsorption performance of the NCS-HSNs prepared by the method comprises the following specific steps:
the test method comprises the following steps: 10mg of GO/NCS-HSNs obtained in the example 4 are added into 50mL of methylene blue solution with the concentration of 20mg/L, sampling is carried out every 30 minutes, then centrifugal separation is carried out, and finally the supernatant is taken and the absorbance of the supernatant is detected by an ultraviolet spectrophotometer, so that the adsorption capacity is obtained. The test results are shown in FIG. 6-a.
It can be seen from FIGS. 6-a and 6-b that the adsorption capacity of NCS-HSNs to methylene blue rapidly increases in the first 60 minutes, then the adsorption rate of NCS-HSNs to methylene blue begins to slow down after adsorption sites on the surface of the composite are gradually occupied, and finally reaches equilibrium in 180 minutes; moreover, after graphene oxide and organic hollow silica are compounded, the adsorption capacity of the compound to methylene blue is obviously higher than that of a single organic hollow silica nano particle and graphene oxide/organic silica nano compound; this shows that, as the adsorbent, the graphene oxide/organic hollow silica nanocomposite has a promoting effect on the adsorption of methylene blue.
In order to more clearly illustrate the advantages of the preparation method of the graphene oxide/organic hollow silica nanocomposite material compared with the prior art, the two technical schemes are compared by workers, and the comparison results are as follows:
Figure BDA0002284571060000181
Figure BDA0002284571060000191
as can be seen from the above table, compared with the prior art, the preparation method of the graphene oxide/organic hollow silica nanocomposite has the advantages of large maximum adsorption capacity, many types of adsorbable substances and high adsorption efficiency.
Example 6
The product prepared in this example was (graphene oxide/ureido hollow silica);
the preparation method is the same as that of example 1; the difference lies in that: the product prepared in this example is a graphene oxide/ureido functionalized hollow silica nanocomposite; the prepared organic hollow silica is carbamido functionalized hollow silica.
And (4) conclusion: the graphene oxide/carbamido hollow silica prepared by the method has excellent adsorption performance; simple operation and environmental protection.
Example 7
The product prepared in this example was (graphene oxide/amino hollow silica);
the preparation method is the same as example 1; the difference lies in that: the product prepared in this example is a graphene oxide/amino functionalized hollow silica nanocomposite; the prepared organic hollow silica is amino functionalized hollow silica.
And (4) conclusion: the graphene oxide/amino hollow silicon dioxide prepared by the method has excellent adsorption performance; simple operation and environmental protection.
Other parts not described belong to the prior art.

Claims (8)

1. The preparation method of the graphene oxide/organic hollow silicon dioxide nano composite material is characterized by comprising the following steps: comprises the following steps of (a) preparing a solution,
the method comprises the following steps: preparing graphene oxide;
step two: preparing organic hollow silica;
preparing an organosilane composition with a core-shell structure by using organosilane with weak alkali resistance and organosilane with strong alkali resistance, and etching by using a NaOH solution to obtain organic hollow silicon dioxide;
step three: preparing a graphene oxide/organic hollow silica nanocomposite;
carrying positive charges on the organic hollow silicon dioxide, and combining the organic hollow silicon dioxide with the graphene oxide with the negative charges to obtain a graphene oxide/organic hollow silicon dioxide nano composite material;
in the second step, the preparation of the organic hollow silica comprises the following steps:
s21: adding 0.3-0.4 mL of vinyl triethoxysilane or 2-cyanopropyltriethoxysilane into a solution containing 40-50 mL of deionized water and 5-10 mL of anhydrous ethanol, and reacting at 35 ℃ for 2-3 h; obtaining a third system;
s22: adding 0.5-1.0 mL of ammonia water into the third system, and reacting for 6-10 h; obtaining a fourth system;
s23: adding 0.4-0.5 mL of 3-thiocyanatopropyltriethoxysilane (TCPTES) into the fourth system, and continuing stirring for 6-8 h; obtaining a second product;
s24: carrying out solid-liquid separation on the second product to obtain a third product;
washing the third product with deionized water and ethanol respectively, and drying the third product in a drying oven at the temperature of 70 ℃ to obtain 2.0-2.5 mg of organic functionalized silicon dioxide with a core-shell structure;
s25: adding the organic functionalized silicon dioxide with the core-shell structure prepared in the S24 into a sodium hydroxide solution with the concentration of 0.5-1.0 mol/L, performing ultrasonic treatment for 5-10 min to disperse the organic functionalized silicon dioxide with the core-shell structure, and reacting at 60 ℃ for 10-12 h; obtaining a fourth product;
s26: and finally, centrifugally separating, washing the fourth product with deionized water and ethanol for multiple times, and drying the fourth product in a drying box at the temperature of 70 ℃ to obtain 0.7-1.2 mg of organic hollow silica.
2. The method for preparing a graphene oxide/organic hollow silica nanocomposite according to claim 1, wherein: in the first step, the preparation of graphene oxide comprises the following steps:
s11: adding 3-9 g of graphite powder, 1-3 g of sodium nitrate and 100-150 mL of concentrated sulfuric acid into a three-neck flask to form a mixed system, controlling the temperature of the system to be lower than 5 ℃, and reacting for 2-3 h under the condition; obtaining a first system;
s12: adding 18-30 g of potassium permanganate into the first system for multiple times within 1 hour, and maintaining the temperature of the first system to be not more than 10 ℃ through an ice water bath;
then mechanically stirring for 1-2 h, converting the ice water bath into a warm water bath, maintaining the temperature of the first system at 35 ℃, and mechanically stirring for 2-4 h; obtaining a second system;
s13: slowly adding 200-300 mL of deionized water into the second system for rapid stirring, and controlling the temperature of the second system not to exceed 90 ℃; stirring for 15-30 min, slowly adding 100-200 mL of hydrogen peroxide into the second system until the system turns to bright yellow; obtaining a first product;
s14: washing the first product with 1.45mol/L diluted hydrochloric acid for several times until no precipitate is generated after the first product is added with barium chloride; washing with water for multiple times until no precipitate is generated when silver nitrate is added into the first product; and finally, freeze-drying the first product to obtain the graphene oxide.
3. The method for preparing a graphene oxide/organic hollow silica nanocomposite according to claim 2, wherein: s11, adding 6g of graphite powder and 3g of sodium nitrate into a three-neck flask; the concentrated sulfuric acid is 150mL; controlling the temperature of the system to be lower than 5 ℃, and reacting for 3 hours in the state;
in S12, 24g of potassium permanganate is added;
in S13, 270mL of deionized water was used.
4. The method for preparing a graphene oxide/organic hollow silica nanocomposite according to claim 1, wherein: in the second step, the organic hollow silica is at least thiocyano functionalized hollow silica or mercapto functionalized hollow silica or ureido functionalized hollow silica or amino functionalized hollow silica.
5. The method for preparing graphene oxide/organic hollow silica nanocomposite according to claim 4, wherein: in step S21, 0.3mL of vinyltriethoxysilane or 2-cyanopropyltriethoxysilane was added;
in step S23, 3-thiocyanatopropyltriethoxysilane was added in an amount of 0.4mL.
6. The method for preparing graphene oxide/organic hollow silica nanocomposite according to claim 5, wherein: in the third step, the graphene oxide/organic hollow silica nanocomposite is prepared, which comprises the following steps:
s31: dispersing 30-60 mg of graphene oxide prepared in the first step in deionized water; then carrying out ultrasonic treatment for 2-3 h under the ultrasonic power of 180-200W; obtaining a first suspension;
s32: dispersing 60-120 mg of the organic hollow silica prepared in the second step in deionized water; then carrying out ultrasonic treatment for 5-10 min under the ultrasonic power of 180-200W; obtaining a second suspension;
then adding concentrated hydrochloric acid with the volume of 0.2-0.4 mL into the second suspension; obtaining a third suspension;
s33: and finally, mixing the first suspension and the third suspension, mechanically stirring for 6-10 hours at 70 ℃, then performing centrifugal separation, and drying the solid to obtain the graphene oxide/organic hollow silica nanocomposite.
7. The method for preparing a graphene oxide/organic hollow silica nanocomposite according to claim 6, wherein: in the third step, the graphene oxide/organic hollow silica nanocomposite is at least graphene oxide/thiocyano functionalized hollow silica nanocomposite or graphene oxide/mercapto functionalized hollow silica nanocomposite or graphene oxide/ureido functionalized hollow silica or graphene oxide/amino functionalized hollow silica.
8. The method for preparing a graphene oxide/organic hollow silica nanocomposite according to claim 7, wherein: in step S32, 120mg of organic hollow silica is dispersed in deionized water;
in step S32, concentrated hydrochloric acid was added in a volume of 0.4mL.
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