CN110055031B - Preparation method of wide ultraviolet visible absorption graphene composite film material - Google Patents
Preparation method of wide ultraviolet visible absorption graphene composite film material Download PDFInfo
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- CN110055031B CN110055031B CN201910449141.4A CN201910449141A CN110055031B CN 110055031 B CN110055031 B CN 110055031B CN 201910449141 A CN201910449141 A CN 201910449141A CN 110055031 B CN110055031 B CN 110055031B
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Abstract
A preparation method of a wide ultraviolet visible absorption graphene composite film material comprises the following steps: weighing 28.3g of phosphoric acid with 85% mass fraction to a constant volume of 250 mL; placing 5mL of 2g of graphene and phosphoric acid solution in a 60 ℃ drying oven for activation for 5 h; filtering and cleaning graphene, drying the graphene to constant weight, and mixing and grinding the graphene and ferrocene according to a molar ratio of 1: 0.5-2; taking 300mg of polyvinyl alcohol, adding 7mL of N, N-dimethylacetamide, heating to 120 ℃, condensing and refluxing for 12h to obtain a polyvinyl alcohol solution; cooling to 97 ℃, adding 70mg of composite material, keeping the temperature, condensing and refluxing for 24 hours to obtain a mixed solution; and transferring the mixed solution to a culture dish or a glass slide, paving the mixed solution, and naturally airing the mixed solution at room temperature for 2 to 3 days to form a film. The preparation method of the wide ultraviolet visible absorption graphene composite film material provided by the invention has a strong absorption effect on ultraviolet visible light with the wavelength of 260-800 nm.
Description
Technical Field
The invention relates to a preparation method of a wide ultraviolet visible absorption graphene composite film material.
Background
Composite materiaLs (composites) are materiaLs with new properties, which are composed of two or more materiaLs with different properties on a macroscopic scale through physical or chemical methods. The various materials complement each other in performance to generate more excellent effect, so that the comprehensive performance of the composite material is superior to that of the original composition material to meet different requirements of various performances.
Graphene, which is considered to be a material with future revolutionary property, has good performance in the aspects of optical properties, mechanical properties, electrical properties and the like, carbon atoms in the graphene are arranged in sp2 hybrid bonding orbitals, each carbon atom in the graphene can enable one unbound electron located on a pz orbit to be dissociated, when the pz orbitals of adjacent atoms form a vertical angle with a plane, a pi bond can be formed, and the formed pi bond is in a half-filled state. However, since graphene is in an inert state, agglomeration is easy to occur, so that the application of graphene in many fields is limited, and graphene can be compounded with materials with different properties to generate more excellent properties to better play a role.
Ferrocene is an organic transition metal compound having aromatic properties, is orange yellow powder at room temperature, and has camphor smell. Because the ferrocene has a larger pi electron conjugated system and stronger internal molecular electron transfer characteristic, the ferrocene has good photoelectric functional property.
The composite material technology has the advantages of designability of structure and capability of carrying out composite structure design, and not only can bear excellent performances among all component materials, but also can achieve comprehensive performances which can not be possessed by a single material according to the combination and the association of performances among different materials.
In the field of light absorption materials and photovoltaic materials, the absorption rate of the light absorption materials or the photovoltaic materials to sunlight is always low due to the lack of strong absorption materials to broadband (260-800nm) ultraviolet visible light, and the photoelectric conversion efficiency of the photovoltaic materials is further influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a strong ultraviolet and visible absorption film material with strong absorption effect on broadband (260-800nm) ultraviolet and visible light.
In order to solve the technical problem, the invention provides a preparation method of a wide ultraviolet-visible absorption graphene composite film material, which comprises the following steps:
(1) weighing 25.5-31.2g of phosphoric acid with the mass fraction of 85%, adding water for dilution, and fixing the volume to 250mL to prepare a phosphoric acid solution;
(2) 2.0g of graphene and 4.5-5.5mL of phosphoric acid solution are mixed and then are placed in an oven with the temperature of 50-70 ℃ for activation for 1.8-2.2 h;
(3) filtering the activated graphene, washing the graphene with distilled water until the pH value of the waste liquid is 7, and drying the graphene in an oven at the temperature of 100-120 ℃ for 1.8-2.2h until the graphene is constant in weight for later use;
(4) mixing the graphene dried in the step (3) with ferrocene according to the molar ratio of 1:0.5-2, and grinding for 1.8-2.2h to obtain a composite material;
(5) adding 7mL of N, N-dimethylacetamide into 300mg of polyvinyl alcohol, heating to 110-;
(6) cooling the polyvinyl alcohol solution obtained in the step (5) to 96-98 ℃, then adding 70mg of the composite material obtained in the step (4), maintaining the heating state, keeping the temperature of the polyvinyl alcohol solution mixed with the composite material at 96-98 ℃, condensing and refluxing for 24h, and stirring with magnetic force of 450-550r/min in the heating process to obtain a mixed solution;
(7) the mixed solution is taken out and laid flat and placed indoors, and the film is formed by natural airing for 2 to 3 days at room temperature.
Preferably, the container material used for grinding in step (4) is agate.
The invention has the advantages that: according to the preparation method of the wide ultraviolet visible absorption graphene composite film material, the wide-band (namely the wavelength of 260-800nm) ultraviolet visible light has a strong absorption effect, and experimental results show that the composite film material prepared by the invention has a good absorption effect on light in a region with the wide ultraviolet visible wavelength of 260-800nm, and can be applied to solar cells as an ideal light absorption material in later energy development, especially in the utilization of solar energy resources.
The material of the container used for grinding is agate, so that the ground graphene and ferrocene can be prevented from reacting with the container.
Drawings
FIG. 1 is an infrared spectrum of a first embodiment of the present invention.
FIG. 2 is an infrared spectrum of a second embodiment of the present invention.
FIG. 3 is an infrared spectrum of a third embodiment of the present invention.
FIG. 4 is a graph of UV-visible absorption according to a first embodiment of the present invention.
FIG. 5 is a graph of UV-visible absorption for example two of the present invention.
FIG. 6 is a graph of UV-visible absorption for example three of the present invention.
FIG. 7 is a photograph of a composite film according to example two of the present invention at 3000 times magnification.
FIG. 8 is a photograph at 6000 times magnification of a composite film according to example two of the present invention.
FIG. 9 is a 12000 Xmagnified photograph of a composite film according to example two of the present invention.
Detailed Description
The first embodiment is as follows:
a preparation method of a wide ultraviolet visible absorption graphene composite film material comprises the following steps:
(1) weighing 25.5g of phosphoric acid with the mass fraction of 85% in a beaker, adding water for dilution, and fixing the volume in a 250mL volumetric flask to prepare a phosphoric acid solution;
(2) weighing 2.0g of graphene in a beaker, weighing 4.5mL of phosphoric acid solution, slowly adding the phosphoric acid solution into the beaker, and then placing the beaker filled with the graphene and the phosphoric acid solution in a drying oven at 50 ℃ for activation for 1.8 h;
(3) filtering the activated graphene, washing the graphene with distilled water until the pH value of waste liquid is 7, and drying the graphene in an oven at 100 ℃ for 1.8h until the graphene is constant in weight for later use;
(4) mixing the graphene and ferrocene dried in the step (3) according to a molar ratio of 2:1, and then pouring the mixture into an agate mortar for grinding for 1.8 hours to obtain a composite material;
(5) weighing 300mg of polyvinyl alcohol into a round-bottom flask, adding 7mL of N, N-dimethylacetamide, heating to 110 ℃, condensing and refluxing for 12h, and stirring with magnetic force of 450r/min in the heating process to obtain a polyvinyl alcohol solution;
(6) after heating is stopped, cooling the polyvinyl alcohol solution to 96 ℃, then adding 70mg of the composite material prepared in the step (4), maintaining the heating state, keeping the temperature of the polyvinyl alcohol solution mixed with the composite material at 96 ℃, condensing and refluxing for 24 hours, and carrying out magnetic stirring at 450r/min in the heating process to obtain a mixed solution;
(7) transferring the mixed solution to a culture dish or a glass slide by a pipette, paving the mixture, placing the mixture in a room, and naturally airing the mixture for 2 to 3 days at room temperature to form a film.
Example two:
a preparation method of a wide ultraviolet visible absorption graphene composite film material comprises the following steps:
(1) weighing 28.3g of phosphoric acid with the mass fraction of 85% in a beaker, adding water for dilution, and fixing the volume in a 250mL volumetric flask to prepare a phosphoric acid solution;
(2) weighing 2.0g of graphene in a beaker, weighing 5mL of phosphoric acid solution, slowly adding the phosphoric acid solution into the beaker, and then placing the beaker filled with the graphene and the phosphoric acid solution in a 60 ℃ drying oven for activation for 2 hours;
(3) filtering the activated graphene, washing the graphene with distilled water until the pH value of waste liquid is 7, and drying the graphene in a drying oven at 110 ℃ for 2h until the graphene is constant in weight for later use;
(4) mixing the graphene and ferrocene dried in the step (3) according to a molar ratio of 1:1, and then pouring the mixture into an agate mortar for grinding for 2 hours to obtain a composite material;
(5) weighing 300mg of polyvinyl alcohol into a round-bottom flask, adding 7mL of N, N-dimethylacetamide, heating to 120 ℃, condensing and refluxing for 12h, and stirring with 500r/min magnetic force in the heating process to obtain a polyvinyl alcohol solution;
(6) after heating is stopped, cooling the polyvinyl alcohol solution to 97 ℃, then adding 70mg of the composite material prepared in the step (4), maintaining the heating state, keeping the temperature of the polyvinyl alcohol solution mixed with the composite material at 97 ℃, condensing and refluxing for 24 hours, and carrying out magnetic stirring at 500r/min in the heating process to obtain a mixed solution;
(7) transferring the mixed solution to a culture dish or a glass slide by a pipette, paving the mixture, placing the mixture in a room, and naturally airing the mixture for 2 to 3 days at room temperature to form a film.
Example three:
a preparation method of a wide ultraviolet visible absorption graphene composite film material comprises the following steps:
(1) weighing 31.2g of phosphoric acid with the mass fraction of 85% in a beaker, adding water for dilution, and fixing the volume in a 250mL volumetric flask to prepare a phosphoric acid solution;
(2) weighing 2.0g of graphene in a beaker, weighing 5.5mL of phosphoric acid solution, slowly adding the phosphoric acid solution into the beaker, and then placing the beaker filled with the graphene and the phosphoric acid solution in a 70 ℃ drying oven for activation for 2.2 h;
(3) filtering the activated graphene, washing the graphene with distilled water until the pH value of waste liquid is 7, and drying the graphene in an oven at 120 ℃ for 2.2h until the graphene is constant in weight for later use;
(4) mixing the graphene and ferrocene dried in the step (3) according to a molar ratio of 1:2, and then pouring the mixture into an agate mortar for grinding for 2.2 hours to obtain a composite material;
(5) weighing 300mg of polyvinyl alcohol into a round-bottom flask, adding 7mL of N, N-dimethylacetamide, heating to 130 ℃, condensing and refluxing for 12h, and stirring with 550r/min magnetic force in the heating process to obtain a polyvinyl alcohol solution;
(6) after heating is stopped, cooling the polyvinyl alcohol solution to 98 ℃, then adding 70mg of the composite material prepared in the step (4), maintaining the heating state, keeping the temperature of the polyvinyl alcohol solution mixed with the composite material at 98 ℃, condensing and refluxing for 24 hours, and carrying out magnetic stirring at 550r/min in the heating process to obtain a mixed solution;
(7) transferring the mixed solution to a culture dish or a glass slide by a pipette, paving the mixture, placing the mixture in a room, and naturally airing the mixture for 2 to 3 days at room temperature to form a film.
In the above examples, the specifications and the production locations of the reagents used are shown in the following table:
| name of reagent | Specification of | Producing area |
| Multilayer graphene | Suzhou carbon feng technology | |
| C10H10Fe | ≥98％ | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| N, N-dimethyl acetamide | Analytical purity | Yongda chemical reagents of Tianjin City |
Structural characterization:
preparing composite material films according to the preparation methods of the wide ultraviolet visible absorption graphene composite film materials described in the first to third embodiments, respectively, performing infrared detection on the composite material films, and characterizing components and structures of the films by an infrared spectrum, wherein experimental results of the first to third embodiments respectively correspond to fig. 1 to 3, and horizontal coordinates in the fig. 1 to 3 are wave numbers (cm, and the same, cm, or a similar to the same or similar to the same reference numerals, except for the same reference numerals, respectively, and the same reference numerals, and the same or similar to the same reference numerals-1) And the ordinate is reflectance (%).
As shown in FIGS. 1-3, 3300cm in the figure-1Is the characteristic absorption peak of the hydroxyl in the middle of the polyvinyl alcohol. 1790cm-1Is a carbonyl characteristic absorption peak of partial oxidation in graphene and is 1500cm-1And a stretching vibration peak of a carbon-carbon bond on a benzene ring in graphene appears nearby. 1000cm-1And 1100cm-1The vicinity is a characteristic peak of ferrocene. The prepared film material contains ferrocene and graphene.
And (3) characterization of absorption performance:
composite material films are prepared according to the preparation method of the wide ultraviolet-visible absorption graphene composite film material described in the first to third embodiments, ultraviolet-visible absorption detection is performed on the composite material films, the absorption intensity of the prepared film material is characterized through the ultraviolet-visible absorption detection, and the experimental results of the first to third embodiments correspond to fig. 4 to 6 respectively, wherein the abscissa of the fig. 4 to 6 is the wavelength (nm), and the ordinate of the fig. 4 to 6 is the absorption intensity (a.u.).
The analysis of fig. 4 to fig. 6 shows that the maximum absorption wavelengths of the composite material film manufactured by the preparation method of the graphene composite film material with wide ultraviolet visible absorption range are 268nm, 295nm and 464nm, and the composite material film has a very strong ultraviolet visible absorption effect in the wavelength range of 260-800nm, so that the composite material has a wide ultraviolet visible absorption range, and the composite film material of the two can be used as a very good ultraviolet visible absorption material.
And (3) SEM (scanning electron microscope) detection:
the composite material films are prepared according to the preparation method of the wide ultraviolet visible absorption graphene composite film material described in the second embodiment, and then are respectively subjected to SEM (scanning electron microscope) detection, the composite material films are sequentially amplified by 3000 times, 6000 times and 12000 times under the SEM, and the crystal morphology of the films and the condition of the crystal surfaces can be clearly seen from the spectrum of the SEM.
SEM micrographs are shown in FIGS. 7-9, and it can be seen from FIG. 7 that the composite material has spherical crystals with uniform particle size of about several hundred nanometers, smooth crystal surface without much hair, and high surface energy. From figure 8, the film surface is relatively smooth, the density is high, and the cross section is clear and smooth; most of ferrocene is dispersed in an active graphene system uniformly, the compatibility is good, and obvious phase separation does not exist; as can be seen from fig. 9, a partially porous microporous structure exists on the membrane surface.
Claims (2)
1. A preparation method of a wide ultraviolet visible absorption graphene composite film material comprises the following steps:
(1) weighing 25.5-31.2g of phosphoric acid with the mass fraction of 85%, adding water for dilution, and fixing the volume to 250mL to prepare a phosphoric acid solution;
(2) 2.0g of graphene and 4.5-5.5mL of phosphoric acid solution are mixed and then are placed in an oven with the temperature of 50-70 ℃ for activation for 1.8-2.2 h;
(3) filtering the activated graphene, washing the graphene with distilled water until the pH value of the waste liquid is 7, and drying the graphene in an oven at the temperature of 100-120 ℃ for 1.8-2.2h until the graphene is constant in weight for later use;
(4) mixing the graphene dried in the step (3) with ferrocene according to the molar ratio of 1:0.5-2, and grinding for 1.8-2.2h to obtain a composite material;
(5) adding 7mL of N, N-dimethylacetamide into 300mg of polyvinyl alcohol, heating to 110-;
(6) cooling the polyvinyl alcohol solution obtained in the step (5) to 96-98 ℃, then adding 70mg of the composite material obtained in the step (4), maintaining the heating state, keeping the temperature of the polyvinyl alcohol solution mixed with the composite material at 96-98 ℃, condensing and refluxing for 24h, and stirring with magnetic force of 450-550r/min in the heating process to obtain a mixed solution;
(7) the mixed solution is taken out and laid flat and placed indoors, and the film is formed by natural airing for 2 to 3 days at room temperature.
2. The preparation method of the wide ultraviolet visible absorption graphene composite film material according to claim 1, characterized in that: and (4) the container material used for grinding in the step (4) is agate.
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| CN103254455A (en) * | 2013-04-23 | 2013-08-21 | 中国科学院上海光学精密机械研究所 | Preparation method of graphene-thickening polymer composite film |
| CN104003627A (en) * | 2014-03-14 | 2014-08-27 | 中国科学院上海光学精密机械研究所 | Preparation method for graphene photonic crystal composite films |
| CN106317578A (en) * | 2016-09-12 | 2017-01-11 | 福州大学 | High-ultraviolet-shielding high-barrier nanomaterial film and preparation method thereof |
| CN107099271A (en) * | 2017-04-07 | 2017-08-29 | 安徽科技学院 | A kind of strong UV, visible light powder body material being combined based on carbon fiber and ferrocene and preparation method thereof |
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