CN111086986B - P-aminoazobenzene functionalized graphene material and preparation method thereof - Google Patents
P-aminoazobenzene functionalized graphene material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a para-aminoazobenzene functionalized graphene material and a preparation method thereof. According to characterization and analysis, azobenzene molecules are successfully grafted on the surface of graphene, the molar grafting rate can reach 10%, and the aminoazobenzene functionalized graphene has a complete surface and is not obviously structurally damaged. The method provides a method and application premise for modifying the surface of the azobenzene material with the graphene.
Description
Technical Field
The invention belongs to the field of nano composite materials, and particularly relates to an aminoazobenzene functionalized graphene material and a preparation method thereof.
Background
Since 2010, graphene materials have excellent electrical and thermal conductivity and stable structures, and therefore, the graphene materials are rapidly developed in various aspects such as energy, machinery, biology, medicine and the like. However, in research, graphene has a simple structure, few surface functional groups and poor dispersibility, so that the graphene is greatly limited in numerous research applications. In order to improve this defect, researchers advocate to perform surface functionalization treatment on graphene, increase the active sites of graphene, change the dispersion performance of graphene, and particularly increase the specific functional groups of graphene, such as amino groups, sulfonic acid groups, hydroxyl groups, and the like, according to the needs. Azobenzene is a common dye, not only is the surface functional group rich, but also the unique isomerization of azobenzene enables azobenzene molecules to be widely applied to the fields of solar energy heat storage and optical control. Azobenzene molecules with amino groups have high activity, and the amino groups on the surface are often used as active functional groups to provide growth sites for the polymerization of various high polymer materials. The technology is widely applied to the aspects of research and development of capacitors, design of anticorrosive materials and the like. Nowadays, the quality of life of people is continuously improved, and the issues of energy storage, environmental friendliness and the like are more and more sensitive, so that the development of energy storage environment-friendly materials is very important. Through long-time research, azobenzene molecules with amino groups can be grafted on the surface of graphene by using a covalent bond functionalization method, and the performances of higher energy storage density, isomerization rate, long half-life period and the like are shown. And the azobenzene functionalized graphene molecule can be compounded with various materials to obtain different graphene composite materials, such as azobenzene functionalized graphene/polyaniline composite materials, azobenzene functionalized graphene/polypyrrole composite materials and the like. Therefore, the preparation method or process of the aminoazobenzene functionalized graphene has great potential in various aspects of energy storage, material corrosion prevention, aerospace equipment development and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a p-aminoazobenzene functionalized graphene material and a preparation method thereof, namely the p-aminoazobenzene functionalized graphene material is prepared, and p-aminoazobenzene molecules are grafted on the surface of graphene in a covalent bond mode.
The technical purpose of the invention is realized by the following technical scheme.
A p-aminoazobenzene functionalized graphene material has a structure shown in the following chemical formula.
Namely, the aminoazobenzene molecules are grafted to the surface of the graphene in a covalent bond mode.
In addition, the graphene is obtained by reducing graphene or graphene oxide (namely, reduced graphene oxide) which is used as a raw material.
The p-aminoazobenzene molecule has a structure represented by the following molecular formula.
The para-aminoazobenzene molecules are grafted to the surface of the graphene in a covalent bond mode, and the molar grafting rate is 10-30%, preferably 20-30%.
The preparation method of the aminoazobenzene functionalized graphene material comprises the following steps:
step 1, synthesis of p-aminoazobenzene monomer (i.e., method for preparing p-aminoazobenzene)
Uniformly dispersing paranitroaniline in concentrated sulfuric acid, adding water for dilution, heating to 70-80 ℃, adding ammonium persulfate for reaction, recrystallizing the precipitate after reaction in glacial acetic acid, and carrying out vacuum drying treatment at 60-70 ℃; dispersing the dried product and sodium sulfide in a mixed solution of deionized water and ethanol, reacting at 80-90 ℃, recrystallizing the reacted precipitate in ethanol, and drying at 60-70 ℃ in vacuum to obtain orange powder, namely, paraaminoazobenzene
In step 1, the molar ratio of ammonium persulfate to p-nitroaniline is (1-5): 1, preferably (2-3): 1.
in step 1, the molar ratio of sodium sulfide to p-nitroaniline is (2-5): 1, preferably (2.5-3): 1.
in the step 1, p-nitroaniline is uniformly dispersed in concentrated sulfuric acid and diluted by adding water, wherein the volume ratio of the water to the concentrated sulfuric acid is (1-5): 1, the concentrated sulfuric acid is sulfuric acid with the mass percentage of 95-98 wt.
In step 1, ammonium persulfate is added for the reaction for 1 to 5 hours, preferably 3 to 5 hours.
In step 1, the reaction is carried out at 80 to 90 ℃ for 1 to 5 hours, preferably 3 to 5 hours.
In step 1, mechanical or ultrasonic stirring is selected during the reaction, and the stirring speed is 100-300 revolutions per minute.
In step 1, in a mixed solution of deionized water and ethanol, the two are in an equal volume ratio.
Step 2, preparing the p-aminoazobenzene functionalized graphene material
Dispersing p-aminoazobenzene and graphene in hydrochloric acid to form a suspension, dropwise adding a sodium nitrite aqueous solution under an ice bath condition, and continuously stirring for reaction to obtain a p-aminoazobenzene functionalized graphene material, wherein the molar ratio of p-aminoazobenzene to sodium nitrite is equal.
In step 2, the ice bath condition is 0-5 ℃.
In step 2, stirring is carried out mechanically or ultrasonically at a speed of 100-500 rpm.
In step 2, the hydrochloric acid is aqueous hydrogen chloride solution with the concentration of 1-5 mol/L.
In step 2, the dropping rate is 1 to 10ml per minute, and the entire reaction time is 10 to 30 hours, preferably 15 to 26 hours.
In the step 2, after the reaction is finished, filtering, and washing with absolute ethyl alcohol and deionized water for 2 times respectively to obtain the p-aminoazobenzene functionalized graphene material.
According to the technical scheme, graphene obtained by reducing graphene oxide is selected as graphene, firstly, graphene oxide suspension is obtained according to a Hummers method or an improved method, then, hydrazine hydrate and nitrogen atmosphere are adopted for reduction, for example, reaction is carried out for 6-8 hours at 80-90 ℃, reduced graphene oxide (namely graphene) is obtained, the method avoids the influence of substances such as sodium borohydride and sodium hydroxide in the previous scheme (such as salt generation), relatively complete graphene structure is obtained, and damage of a benzene ring structure of the graphene caused by oxidation treatment is avoided. In the process of preparing the p-aminoazobenzene functionalized graphene material, a method of firstly dispersing reaction substances (p-aminoazobenzene and graphene) and then dropwise adding sodium nitrite is adopted, so that all the participating substances are effectively reacted, azobenzene salt and amide bonding benzene rings are formed almost simultaneously, the overall reaction efficiency is improved, and the defects of insufficient reaction, graft of azobenzene salt and the like, in the conventional scheme, namely the defects of firstly forming azobenzene salt and then adding graphene for reaction, are overcome. The prepared graphene material with functionalized aminoazobenzene has the performances of graphene and azobenzene molecules, can be used for heat storage materials, high-molecular-structure framework materials, photoinduced deformation and the like in the future, and has wide application prospects.
Drawings
FIG. 1 is the nuclear magnetic resonance spectrum of p-aminoazobenzene prepared by the present invention.
FIG. 2 is a scanning electron microscope photograph of the p-aminoazobenzene functionalized graphene prepared by the invention.
FIG. 3 is an infrared spectrum of a para-aminoazobenzene functionalized graphene prepared by the method.
Fig. 4 is an XPS spectrum (1) of the para-aminoazobenzene functionalized graphene prepared by the present invention.
Fig. 5 is an XPS spectrum (2) of the para-aminoazobenzene functionalized graphene prepared by the present invention.
Detailed Description
The following embodiments are further detailed, but are not intended to limit the scope of the present invention. Mechanical stirring is adopted in the reaction, and the speed is 200 revolutions per minute; the dropping speed is 10ml per minute; controlling the ice bath temperature to be 0-4 ℃.
Example 1
1) Synthesis of p-aminoazobenzene monomer: dispersing 10g of p-nitroaniline in 80mL of concentrated sulfuric acid, slowly adding the solution into 160mL of deionized water for dilution, raising the temperature to 70 ℃, slowly adding ammonium persulfate with the molar weight being 3 times that of the p-nitroaniline, continuously reacting for 5 hours, recrystallizing the precipitate in glacial acetic acid, and drying the product in vacuum at 70 ℃ for 24 hours. And then dispersing the product and sodium sulfide with the molar weight 2.5 times that of p-nitroaniline in a mixed solution of deionized water and ethanol (equal volume ratio), reacting for 3h at 85 ℃, recrystallizing the precipitate in ethanol, and then drying in vacuum at 70 ℃ for 24h to obtain orange powder, namely p-aminoazobenzene.
2) Preparing an aminoazobenzene functionalized graphene material: with the diazotization reaction, 1.5g of p-aminoazobenzene was first dispersed in 100mL of 1mol/L hydrochloric acid solution, treated with ice bath for 1h, and then the graphene material was dispersed in the above mixed solution and reacted for 2 h. And then, dissolving sodium nitrite with the same molar weight as the p-aminoazobenzene in deionized water, slowly dropwise adding the sodium nitrite into the mixed solution, and continuously reacting for 24 hours in ice bath after the dropwise adding is finished. And after the reaction is finished, filtering, washing with absolute ethyl alcohol and deionized water for 2 times respectively, and drying in vacuum at 80 ℃ to obtain the aminoazobenzene functionalized graphene material.
Example 2
1) Synthesis of p-aminoazobenzene monomer: dispersing 15g of p-nitroaniline in 100mL of concentrated sulfuric acid, slowly adding 150mL of deionized water for dilution, raising the temperature to 70 ℃, slowly adding ammonium persulfate with the molar weight 5 times that of the p-nitroaniline, continuously reacting for 1h, recrystallizing precipitates in glacial acetic acid, and drying the product in vacuum at 70 ℃ for 24 h. And then dispersing the product and sodium sulfide with the molar weight 5 times that of p-nitroaniline in a mixed solution of deionized water and ethanol (equal volume ratio), reacting for 5 hours at 85 ℃, recrystallizing the precipitate in ethanol, and then drying in vacuum for 24 hours at 70 ℃ to obtain orange powder, namely p-aminoazobenzene.
2) Preparing an aminoazobenzene functionalized graphene material: with the diazotization reaction, 2g of p-aminoazobenzene was first dispersed in 80mL of 1mol/L hydrochloric acid solution, and then the graphene material was dispersed in the above mixed solution and reacted for 3 hours. And then, dissolving sodium nitrite with the same molar weight as the p-aminoazobenzene in deionized water, slowly dropwise adding the sodium nitrite into the mixed solution, and continuously reacting for 24 hours in ice bath after the dropwise adding is finished. And after the reaction is finished, filtering, washing with absolute ethyl alcohol and deionized water for 2 times respectively, and drying in vacuum at 80 ℃ to obtain the p-aminoazobenzene functionalized graphene material.
Example 3
1) Synthesis of p-aminoazobenzene monomer: dispersing 10g of p-nitroaniline in 80mL of concentrated sulfuric acid, slowly adding 160mL of deionized water for dilution, raising the temperature to 70 ℃, slowly adding ammonium persulfate with the molar weight 2 times that of the p-nitroaniline, continuously reacting for 3 hours, recrystallizing the precipitate in glacial acetic acid, and drying the product in vacuum at 70 ℃ for 24 hours. And then dispersing the product and sodium sulfide with the molar weight being 3 times that of p-nitroaniline in a mixed solution of deionized water and ethanol (equal volume ratio), reacting for 5 hours at 85 ℃, recrystallizing the precipitate in ethanol, and then drying in vacuum for 24 hours at 70 ℃ to obtain orange powder, namely the p-aminoazobenzene.
2) Preparing an aminoazobenzene functionalized graphene material: with the diazotization reaction, 1.5g of p-aminoazobenzene was first dispersed in 100mL of a 1mol/L hydrochloric acid solution, and then the graphene material was dispersed in the above mixed solution and reacted for 3 hours. And then, dissolving sodium nitrite with the same molar weight as the p-aminoazobenzene in deionized water, slowly dropwise adding the sodium nitrite into the mixed solution, and continuously reacting for 24 hours in ice bath after the dropwise adding is finished. And after the reaction is finished, filtering, washing with absolute ethyl alcohol and deionized water for 2 times respectively, and drying in vacuum at 80 ℃ to obtain the aminoazobenzene functionalized graphene material.
The method for characterizing aminoazobenzene and aminoazobenzene functionalized graphene is described in example 1. As shown in FIG. 1, the apparatus used for the test was a nuclear magnetic resonance analyzer of Varian corporation. As can be seen from the figure, the spectrum has three peaks, and the value of delta-6.27 is p-aminoazobenzene-NH2The vibration peak is 6.83(t,2H), 8.06(t,2H) is the vibration peak of H on the benzene ring of azobenzene, and the nuclear magnetic results prove that the para-aminoazobenzene material is successfully prepared. As shown in fig. 2, it can be clearly seen that the graphene nanosheet is transparent and has a clear fold form, which proves that the graphene oxide in the new process is very thin and has a large specific surface area, the graphene structure is not damaged by agglomeration and the like after functionalization, and the structure is complete. This also directly proves that the preparation effect of graphene is more remarkable under the process of the invention. FIG. 3 is an FTIR chart of graphene G and p-aminoazobenzene functionalized graphene G-PAZO, from which it can be seen that the spectrum of G and G-PAZO is 3400cm-1Has an absorption peak and is graphiteO-H stretching vibration peak of alkene, 1730cm-1A stretching vibration peak of 1626cm-1Peak of stretching vibration of C ═ C, 1356cm-1Flexural vibration peak at N ═ N, 1147cm-1Is a stretching vibration peak of-C-N-, and the N element is from azobenzene, thereby proving that G-PAZO is successfully prepared. XPS is a characterization method used to determine the elemental and elemental content composition of a sample. As can be seen from FIG. 4, the prepared material has C, N elements, FIG. 5 is a graph of the N element peak effect of the aminoazobenzene functionalized graphene G-PAZO, the integral area of all N elements is used as a denominator, and the corresponding-NH in the N elements2The integrated area of the partial peaks of (a) is the molecule, and the molar grafting ratio is calculated. As can be seen from the figure, the peaks of the nitrogen-containing compound can be decomposed into four peaks of 398.8eV, 399.6eV, 400.3eV and 401.7eV, corresponding to aniline (═ N-), quinoid amine (-NH-), and nitrogen cation radical (NH-), respectively+) And amino cation (-NH)2). The elemental content was calculated using the following formula: wherein
is-NH2Integral area of (S)NIs the integrated area of the N element. The calculated data N ═ 0.108/1 × 100% ═ 10.8% were substituted, and therefore the (molar) graft ratio of azo was judged to be about 10.8%.
The preparation of the material can be realized by adjusting the process parameters according to the content of the invention, and the material shows the performance basically consistent with the invention, namely the grafting rate can reach 10-30%. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (7)
1. A p-aminoazobenzene functionalized graphene material is characterized by having a structure shown in the following chemical formula, wherein p-aminoazobenzene molecules are grafted to the surface of graphene in a covalent bond mode, and the molar grafting rate is 10-30%;
the para-aminoazobenzene molecule has a structure shown in the following molecular formula:
step 1, synthesizing a p-aminoazobenzene monomer
Uniformly dispersing paranitroaniline in concentrated sulfuric acid, adding water for dilution, heating to 70-80 ℃, adding ammonium persulfate for reaction, recrystallizing the precipitate after reaction in glacial acetic acid, and carrying out vacuum drying treatment at 60-70 ℃; dispersing the dried product and sodium sulfide in a mixed solution of deionized water and ethanol, reacting at 80-90 ℃, recrystallizing the reacted precipitate in ethanol, and drying at 60-70 ℃ in vacuum to obtain orange powder, namely, paraaminoazobenzene;
step 2, preparing the p-aminoazobenzene functionalized graphene material
Dispersing p-aminoazobenzene and graphene in hydrochloric acid to form a suspension, dropwise adding an aqueous solution of sodium nitrite in the suspension under an ice bath condition, and continuously stirring for reaction to obtain a p-aminoazobenzene functionalized graphene material, wherein the molar ratio of p-aminoazobenzene to sodium nitrite is equal.
2. The p-aminoazobenzene functionalized graphene material according to claim 1, wherein graphene is a raw material graphene, or graphene obtained by reducing graphene oxide with hydrazine hydrate is selected.
3. The p-aminoazobenzene functionalized graphene material according to claim 1 or 2, wherein p-aminoazobenzene molecules are grafted to the surface of graphene in a covalent bond mode, and the molar grafting ratio is 20-30%.
4. A preparation method of an aminoazobenzene functionalized graphene material is characterized by comprising the following steps:
step 1, synthesizing a p-aminoazobenzene monomer
Uniformly dispersing paranitroaniline in concentrated sulfuric acid, adding water for dilution, heating to 70-80 ℃, adding ammonium persulfate for reaction, recrystallizing the precipitate after reaction in glacial acetic acid, and carrying out vacuum drying treatment at 60-70 ℃; dispersing the dried product and sodium sulfide in a mixed solution of deionized water and ethanol, reacting at 80-90 ℃, recrystallizing the reacted precipitate in ethanol, and drying at 60-70 ℃ in vacuum to obtain orange powder, namely p-aminoazobenzene;
step 2, preparing the p-aminoazobenzene functionalized graphene material
Dispersing p-aminoazobenzene and graphene in hydrochloric acid to form a suspension, dropwise adding a sodium nitrite aqueous solution under an ice bath condition, and continuously stirring for reaction to obtain a p-aminoazobenzene functionalized graphene material, wherein the molar ratio of p-aminoazobenzene to sodium nitrite is equal.
5. The method for preparing the p-aminoazobenzene functionalized graphene material according to claim 4, wherein in the step 1, the molar ratio of ammonium persulfate to p-nitroaniline is (1-5) to 1; the molar ratio of the sodium sulfide to the paranitroaniline is (2-5) to 1; uniformly dispersing paranitroaniline in concentrated sulfuric acid, and adding water to dilute, wherein the volume ratio of the water to the concentrated sulfuric acid is (1-5) to 1, and the concentrated sulfuric acid is 95-98 wt% of sulfuric acid in mass percentage; in the mixed solution of deionized water and ethanol, the two are in equal volume ratio.
6. The method for preparing the p-aminoazobenzene functionalized graphene material according to claim 4, wherein in the step 1, ammonium persulfate is added for reaction for 1-5 hours; reacting for 1-5 hours at 80-90 ℃; mechanical or ultrasonic stirring is selected during the reaction, and the stirring speed is 100-300 revolutions per minute.
7. The method for preparing the p-aminoazobenzene functionalized graphene material according to claim 4, wherein in the step 2, the ice bath condition is 0-5 ℃; stirring mechanically or ultrasonically at a speed of 100-500 rpm; hydrochloric acid is aqueous solution of hydrogen chloride with the concentration of 1-5 mol/L; the dropping speed is 1-10 ml per minute, and the whole reaction time is 10-30 hours.
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