TWI743678B - Graphene oxide-ferrum composite film, and the use thereof - Google Patents

Abstract

Provided is a method for preparing a graphene oxide-ferrum composite film, to solve problems existing in the conventional methods that may not prepare graphene oxide film able to maintain stable structure thereof as soaking in the solution, comprising steps of preparing a graphene oxide solution; mixing a ferrous ion salt with the graphene oxide solution in a weight ratio of from 1:4 to 1:8, to obtain a mixed solution; pumping the mixed solution, to obtain a black film; and drying the black film to obtain the graphene oxide-ferrum composite film. A graphene oxide-ferrum composite film comprises a plurality of graphene oxide-ferrum composite film layers and ferrous ions. The ferrous ions are connected to hydroxyl group, epoxy group, carbonyl group, and carboxyl group existing on the surface of each graphene oxide-ferrum composite film layer. A use of graphene oxide-ferrum composite film for removing pollutants from wastewater.

Description

Graphene oxide-iron composite film and its use

The present invention relates to a composite film, especially a graphene oxide-iron composite film; the present invention also relates to a preparation method, especially a preparation method of a graphene oxide-iron composite film; the present invention also relates to a use, especially A use of graphene oxide-iron composite film.

Graphene is a carbon material with a two-dimensional planar structure composed of a single layer of carbon atoms with sp ² bonding. It has excellent mechanical strength, thermal conductivity, electron mobility, transmittance, and high specific surface area. It has both the properties of metal and semiconductor. Graphene oxide (GO) is a graphene material with functional groups such as hydroxyl (OH), epoxy (CO), carbonyl (C=O) and carboxylic acid (COOH) on the surface. Or other carbon sources are prepared by top-down methods such as mechanical stripping, arc discharge, and liquid phase stripping. Graphene oxide not only retains the excellent properties of the original graphene, but also has the possibility of improving its hydrophilicity and bonding with other compounds. In addition, graphene oxide can be used to prepare reduced graphene oxide or modified graphene by heating, adding a reducing agent, or molecular modification, so as to broaden its application range and treat more types of environmental pollutants.

Since graphene oxide has a stable water dispersibility and a high aspect ratio structure, it can be removed by filtration, coating, layer-by-layer adsorption (layer-by-layer adsorption, LbL) assembly, and evaporation methods. Alkene is prepared into graphene oxide film. The interlayer spacing of the graphene oxide film is about 1 nanometer, which is enough to accommodate a single layer of water molecules. Therefore, the interlayer spacing of nanometer wool The thin channels allow water molecules to pass through and screen out small-molecule pollutants in the water. In addition, based on the high specific surface area of graphene oxide itself and the functional groups on the surface area can adsorb or bind pollutants in water, the graphene oxide film can remove inorganic or organic pollution in water by two mechanisms: filtration and adsorption. In order to achieve the effect of purifying water quality.

However, because the functional groups on the surface of the graphene oxide have high hydrophilic properties, when the graphene oxide film prepared by the conventional method is in contact with water, the problem of water molecules intercalating between the layers of the graphene oxide film is likely to occur. , Thereby destroying the structure of the graphene oxide film, causing the graphene oxide film to collapse. Generally speaking, the conventional graphene oxide film will be dispersed into a suspension solution after being placed in water for 24 hours, making it impossible to practically apply to water purification.

In view of this, there is indeed a need to improve the conventional methods for improving the preparation of graphene oxide films.

In order to solve the above problems, the object of the present invention is to provide a method for preparing a graphene oxide-iron composite film by mixing iron with a graphene oxide aqueous solution in a specific ratio, and through the steps of suction filtration and drying to make the iron The ions combine with the oxygen on the hydroxyl, epoxy, carbonyl and carboxyl groups on the surface of each graphene oxide layer to enhance the compactness and structural stability of the graphene oxide-iron composite film, and to extend the graphite oxide The purpose of the service life of the ene-iron composite film.

The second purpose of the invention is to provide a graphene oxide-iron composite film that combines iron ions with the hydroxyl, epoxy, carbonyl and carboxyl groups on the surface of each graphene oxide layer to support each graphene oxide The layer structure achieves the purpose of improving the structure compactness and structural stability of the graphene oxide-iron composite film.

Another object of the invention is to provide a graphene oxide-iron composite film for removing pollutants in wastewater, so as to achieve the purpose of removing pollutants in wastewater.

The use of the quantifier "one" or "one" in the elements and components described in the full text of the present invention is only for the convenience of use and to provide the general meaning of the scope of the present invention; in the present invention, it should be interpreted as including one or at least one, and single The concept of also includes the plural, unless it clearly implies other meanings.

The invention provides a method for preparing a graphene oxide-iron composite film, which includes the following steps: preparing a graphene oxide aqueous solution; mixing a ferrous ion salt with the graphene oxide aqueous solution, and the total iron ions in the ferrous ion salt The weight ratio of the graphene oxide to the graphene oxide in the graphene oxide aqueous solution ranges from 1:4 to 1:8 to obtain a mixed solution; the mixed solution is poured into an air extraction device for air extraction to remove water and obtain A black film; and drying the black film to obtain a graphene oxide-iron composite film.

According to this, by using a specific ratio of iron and graphene oxide aqueous solution to mix, and through the steps of suction filtration and drying, the resulting graphene oxide-iron composite film can be stably grafted based on iron bridging to produce better The stable structure can prolong the service life of the graphene oxide-iron composite film.

Wherein, the weight ratio of the total iron ions in the ferrous ion salt to the graphene oxide in the graphene oxide aqueous solution ranges from 1:5 to 1:7. In this way, a graphene oxide-iron composite film with a tighter and more stable structure and sufficient flexibility can be obtained, thereby prolonging the service life of the graphene oxide-iron composite film.

Wherein, the ferrous ion salt includes ferrous sulfate, ferrous chloride or ferrous nitrate. In this way, a stable grafted and more stable graphene oxide-iron composite film can be obtained, thereby prolonging the service life of the graphene oxide-iron composite film.

Wherein, the step of pouring the mixed solution to an air extraction device for pumping further includes the step of pouring the mixed solution onto a filter paper and shaking to make the liquid level level. In this way, a graphene oxide-iron composite film with a tighter and more stable structure can be obtained, thereby extending the graphene oxide-iron composite film The service life of the membrane.

The present invention also provides a graphene oxide-iron composite film prepared by a method for preparing a graphene oxide-iron composite film, comprising a plurality of graphene oxide layers and iron ions, wherein the functional surface of each graphene oxide layer The group includes a hydroxyl group, an epoxy group, a carbonyl group, and a carboxyl group, and the iron ion is combined with the hydroxyl group, the epoxy group, the carbonyl group, and the oxygen on the carboxyl group. The graphene oxide-iron composite film has a temperature ranging from 45 degrees to Water contact angle between 55 degrees. In this way, iron ions can be combined with the oxygen on the hydroxyl, epoxy, carbonyl, and carboxyl groups on the surface of each graphene oxide layer to support the structure of each graphene oxide layer to improve the graphene oxide-iron composite The structure of the film is compact and stable, and the purpose of extending the service life of the graphene oxide-iron composite film can achieve the effect of the graphene oxide-iron composite film having high fluidity for water molecules.

Among them, the interlayer spacing of each graphene oxide-iron composite film is between 7Å and 7.8Å. In this way, a graphene oxide-iron composite film with a more compact and stable structure can be obtained, thereby prolonging the service life of the graphene oxide-iron composite film.

Among them, the graphene oxide-iron composite film has a water contact angle of 49 degrees. In this way, the graphene oxide-iron composite film can achieve the effect of having high fluidity for water molecules.

The present invention also provides a use of the graphene oxide-iron composite film prepared by the method for preparing the graphene oxide-iron composite film for removing pollutants in wastewater. In this way, the purpose of removing pollutants in wastewater can be achieved.

Among them, the pollutants include chlorpheniramine or methyl blue. In this way, the purpose of removing drugs or chemical pollutants in wastewater can be achieved.

S1: Steps to prepare graphene oxide aqueous solution

S2: Steps to obtain a mixed solution

S3: Steps to obtain a black film

S4: Steps to obtain graphene oxide-iron composite film

[Figure 1] The flow chart of the preparation method of the graphene oxide-iron composite film of the present invention.

[Figure 2A] A photo of a graphene oxide aqueous solution prepared by conventional technology.

[Figure 2B] A photograph of the mixed solution obtained during the preparation of the graphene oxide-iron composite film of the present invention.

[Figure 2C] A photo of a filter paper with a second black clay-like film obtained during the preparation of the graphene oxide-iron composite film of the present invention.

[Figure 2D] A photograph of the graphene oxide-iron composite film of the present invention.

[Figure 3] The graphene oxide-iron composite film of the present invention is used to detect the intensity of the D peak and the G peak using a Raman spectrometer (HORIBA HR800).

[Figure 4A] A photograph of the surface appearance of the graphene oxide-iron composite film of the present invention.

[Figure 4B] A photograph of the distribution of iron elements in the graphene oxide-iron composite film of the present invention.

[Figure 4C] The graphene oxide-iron composite film of the present invention shows the ratio content of carbon, oxygen and iron.

[Figure 4D] The graphene oxide-iron composite film of the present invention uses Fourier-transform infrared spectroscopy (FTIR) to detect the functional groups of the graphene oxide-iron composite film.

[Figure 5A] The graphene oxide-iron composite film of the present invention was observed using a scanning electron microscope (SEM, model SUPRA 55, CARL ZEISS, Germany) at 30x and 1,000x magnifications- Photograph of the surface roughness of the iron composite film.

[Figure 5B] After acid treatment of the graphene oxide-iron composite film of the present invention, the surface roughness of the acid-treated graphene oxide-iron composite film was observed with a scanning electron microscope at 30 times and 1,000 times magnification Of photos.

[Figure 6] The conventional original graphene oxide film and the graphene oxide-iron composite film of the present invention are treated with deionized water, oxidant, acid (pH 1.2) or alkali (pH 10.8), and then used X-ray Shot points X-ray diffraction analysis (XRD, Bruker D8) original graphene oxide film, original graphene oxide-iron composite film, graphene oxide-iron composite film treated with deionized water, graphene oxide treated with oxidant- Graphite lattice characteristics of iron composite film, graphene oxide-iron composite film treated with acid, and graphene oxide-iron composite film treated with alkali. Among them, the curves (a) to (f) represent the original graphene oxide film, the original graphene oxide-iron composite film, the graphene oxide-iron composite film treated with deionized water, and the graphene oxide-iron composite film treated with an oxidant. Composite film, acid-treated graphene oxide-iron composite film and alkali-treated graphene oxide-iron composite film.

[Figure 7] The conventional original graphene oxide film and the graphene oxide-iron composite film of the present invention are immersed in deionized water, acid (pH 1.2) or lye (pH 10.8), the original graphene oxide film Photographs of original graphene oxide-iron composite film, graphene oxide-iron composite film treated with deionized water, graphene oxide-iron composite film treated with acid, and graphene oxide-iron composite film treated with alkali.

In order to make the above and other objects, features and advantages of the present invention more comprehensible, the preferred embodiments of the present invention will be described in detail in conjunction with the accompanying drawings as follows: Please refer to Figure 1. It is the preparation method of the graphene oxide-iron composite film of the present invention, which may include step S1, step S2, step S3, and step S4: prepare a graphene oxide aqueous solution (step S1); combine a ferrous ion salt with the The graphene oxide aqueous solution is mixed, wherein the weight ratio of the total iron ions in the ferrous ion salt to the graphene oxide in the graphene oxide aqueous solution ranges from 1:4 to 1:8 to obtain a mixed solution (step S2 ); Pour the mixed solution to an air extraction device for air extraction to remove moisture and obtain a black film (step S3); and, dry the black film to obtain a graphene oxide-iron composite film (Step S4).

In detail, in step S3, the mixed solution is poured on a filter paper and shaken to make the liquid level level before pumping. In step S4, the black film is placed in a temperature range of 50°C to 60°C. Dry in an oven at ℃.

In this embodiment, by using a specific ratio of iron and graphene oxide aqueous solution to mix, and through the steps of suction filtration and drying, the resulting graphene oxide-iron composite film has a more compact and stable structure, and is resistant to water The molecules have high fluidity, thereby prolonging the service life of the graphene oxide-iron composite film.

In a specific embodiment, the weight ratio of the total iron ions in the ferrous ion salt to the graphene oxide in the graphene oxide aqueous solution ranges from 1:5 to 1:7.

In a specific embodiment, the ferrous ion salt includes ferrous sulfate, ferrous chloride, or ferrous nitrate.

In a specific embodiment, the graphene oxide-iron composite film prepared by the method for preparing the graphene oxide-iron composite film of the present invention includes a plurality of graphene oxide layers and iron ions, wherein each of the graphene oxide layers The functional groups on the surface include a hydroxyl group, an epoxy group, a carbonyl group and a carboxyl group, and the iron ion is combined with the hydroxyl group, the epoxy group, the carbonyl group and the oxygen on the carboxyl group.

In a specific embodiment, the interlayer spacing of each graphene oxide-iron composite film is between 7 Å and 7.8 Å.

In a specific embodiment, the graphene oxide-iron composite film has a water contact angle between 45 degrees and 55 degrees. In another specific embodiment, the graphene oxide-iron composite film has a water contact angle of 49 degrees.

In a specific embodiment, the graphene oxide-iron composite film can be used to remove pollutants in wastewater. In another specific embodiment, the pollutant includes chlorpheniramine or methyl blue.

In this embodiment, the graphene oxide-iron composite film with high surface area adsorption characteristics and fine pores (about 10 Å) sieving characteristics can effectively remove methyl blue or chloropheniramine solution in the methyl blue solution Chlorpheniramine within.

In order to verify that the preparation method of the graphene oxide-iron composite film provided in this case can indeed improve the obtained graphene oxide-iron composite film by adding a specific proportion of ferrous ions and the technical means of vacuum filtration For its stability and adsorption efficiency, the following tests are carried out:

[Preparation Example 1]

Place 1 gram of graphite powder and 0.5 gram of sodium nitrate in a mortar and grind into powder, then pour the powder into a beaker containing 23 ml of concentrated sulfuric acid in an ice bath, and stir slowly with a magnet for 15 minutes. Add 3 grams of ground potassium permanganate powder into the beaker in batches, then place the beaker in an oil bath and stir with a magnet at 35° C. for 2 hours. Place the beaker in an ice bath and add 46 ml of deionized water to change the color of graphite from gray to brown. The beaker was placed in an oil bath, and reacted at 80°C for 15 minutes and then cooled to room temperature; then 10 ml of hydrogen peroxide was slowly added to the beaker to obtain a yellow liquid. Use 80Mpa negative pressure for vacuum filtration to obtain a yellow paste. After washing twice with 10% hydrochloric acid and deionized water, the washed yellow paste is combined with 10 ml of hydrochloric acid and 70 ml of deionized water. The dialysate prepared by water is mixed to obtain a brown mixed liquid. The mixed liquid is poured into the dialysis membrane and placed in a container containing deionized water for dialysis. When the pH of the deionized water in the container is The value is neutral, and the color of the mixture will change to black. The black mixture was oscillated with probe ultrasound for 30 minutes, and then centrifuged at 2,000 rpm for 10 minutes to separate the precipitated graphite with incomplete oxidation. Finally, the suspension was collected to obtain a concentration of 5,000 mg as shown in Figure 2A. /L of graphene oxide aqueous solution.

[Preparation Example 2]

Pour the graphene oxide aqueous solution onto a filter paper with a pore size of less than 5 microns and a diameter of 110 mm, and shake to make the liquid surface level, and then use the evaporation method to remove the water to obtain the filter paper with the first black clay-like film. The filter paper with the first black clay-like film is placed in an oven at 60° C. for drying to obtain a graphene oxide film.

[Preparation Example 3]

0.139 g of ferrous sulfate (FeSO ₄ ‧7H ₂ O) was dissolved in 5 ml of deionized water to obtain a ferrous sulfate solution. The ferrous sulfate solution was mixed with 40 ml of the graphene oxide aqueous solution, and the amount was quantified to 50 ml with deionized water, stirred for 20 seconds, and then allowed to stand for 10 minutes to obtain the mixed solution as shown in Figure 2B. Pour 40 ml of this mixed solution onto a filter paper with a pore size of less than 5 microns and a diameter of 110 mm, and shake to make the liquid level level, and then use an air extraction device to pump air to remove water, and the result is as shown in Figure 2C. Shown is a filter paper with a second black clay-like membrane. Place the filter paper with the second black clay-like film in an oven at 60°C for drying to obtain the graphene oxide-iron composite film as shown in Figure 2D.

[Example 1]

Use Raman spectrometer (HORIBA HR800) to detect the ratio of D peak to G peak (I _D /I _G ) of the graphene oxide-iron composite film. As shown in Figure 3, the D peak appears at 1333 cm ^-1 , which represents graphite The characteristic peak of ene defects and the disorder of atomic arrangement; the G peak appears ^{near 1597.68 cm -1} and is ^{the characteristic peak of sp 2} hybrid carbon atom content. The I _D /I _G ratio of the graphene oxide-iron composite film is about 1.01, the results show that during the process of preparing the graphene oxide-iron composite film, the graphene oxide is not reduced, and the graphene oxide-iron composite film still retains oxygen-containing functional groups.

[Example 2]

Use scanning electron microscope (SEM, model SUPRA 55, CARL ZEISS, Germany) to observe the surface of graphene oxide-iron composite film, and use energy-dispersive X-ray spectroscopy (energy-dispersive X-ray spectroscopy) , EDX), using extra high tension (EHT) of 5.00kV and collection time of 60 seconds to analyze the elemental composition of the graphene oxide-iron composite film. Figures 4A and 4B respectively show the surface state of the graphene oxide-iron composite film and the distribution of iron elements, and the ratio of titanium, oxygen and iron contained in the graphene oxide-iron composite film is shown in Figure 4C They were 57.8%, 33.2% and 9% respectively.

Use Fourier-transform, infrared spectroscopy, FTIR to detect the functional groups of the graphene oxide-iron composite film. As shown in the 4D diagram, the O-Fe tensile vibration peak is measured ^{at 600 cm-1.} , CO tensile vibration peak measured at 1045 cm ^-1 , CC (in-ring) tensile vibration peak measured ^{at 1400 cm-1} , sp ² C=C tensile vibration peak ^{measured at 1610 cm-1} , -C=O tensile vibration peak measured at 1715 cm ^-1 , OH (carboxyl) tensile vibration peak measured ^{at 3190 cm-1} , and OH (alcohol group) tensile measured ^{at 3410 cm-1} The results show that the graphene oxide-iron composite film has a ring structure. The O-Fe tensile vibration peaks confirm that iron ions have indeed been grafted to the graphene oxide-iron composite film, and the graphene oxide-iron composite film The preparation process still retains oxygen-containing functional groups, that is, graphene oxide has not been reduced.

[Example 3]

Use graphene oxide-iron composite film with deionized water, 1.75% v/v hydrogen peroxide solution, acid solution of sulfuric acid solution (pH 3) or alkali solution of sodium hydroxide (pH 10) under 80Mpa negative pressure Vacuum filtration was performed for 150 minutes to obtain graphene oxide-iron composite film treated with deionized water, graphene oxide-iron composite film treated with oxidant, graphene oxide-iron composite film treated with acid, and graphene oxide-iron composite film treated with acid. Alkaline-treated graphene oxide-iron composite film.

Use scanning electron microscope (SEM, model SUPRA 55, CARL ZEISS, Germany) to observe the original graphene oxide-iron composite film at 30 times, 1,000 times, 3,000 times, and 30,000 times magnification, after deionization Surface appearance of graphene oxide-iron composite film treated with water, graphene oxide-iron composite film treated with oxidant, graphene oxide-iron composite film treated with acid, and graphene oxide-iron composite film treated with alkali And thickness. Figure 5A shows the surface appearance of the original graphene oxide-iron composite film observed at 30 times and 1,000 times magnification, and the thickness of the original graphene oxide-iron composite film is 7.59 μm. The surface appearance of graphene oxide-iron composite film treated with deionized water, graphene oxide-iron composite film treated with oxidant, and graphene oxide-iron composite film treated with alkali and original graphene oxide-iron composite film Of There is no significant difference in the surface appearance (results not shown); however, as shown in Figure 5B, compared to the surface appearance of the original graphene oxide-iron composite film, the acid was observed at 30 times and 1,000 times magnification. The edge of the surface layer of the processed graphene oxide-iron composite film is curled and cracks appear. In addition, as shown in Table 1, the graphene oxide-iron composite film treated with deionized water, the graphene oxide-iron composite film treated with oxidant, the graphene oxide-iron composite film treated with acid, and the graphene oxide-iron composite film treated with alkali The thickness of the graphene oxide-iron composite film is 6.36μm, 9.27μm, 6.29μm and 6.36μm, respectively.

[Example 4]

Use X-ray diffraction analysis (XRD, Bruker D8) to observe the original graphene oxide film, the original graphene oxide-iron composite film, the graphene oxide-iron composite film treated with deionized water, and the Analysis of the graphene lattice characteristics of graphene oxide-iron composite film treated with oxidant, graphene oxide-iron composite film treated with acid, and graphene oxide-iron composite film treated with alkali. As shown in Figure 6, the curve (a) shows that the graphite diffraction angle (2θ) of the original graphene oxide film is 11.025 degrees, and the layer spacing (d-spacing) of the graphene oxide film is calculated to be about 8.0 Å using the Bragg equation. . The curve (b) shows that the graphite diffraction angle (2θ) of the original graphene oxide-iron composite film is 11.548 degrees, and the interlayer spacing of the graphene oxide-iron composite film is calculated using the Bragg equation to be about 7.6Å, which is obviously compared to the penetration The graphene oxide film made by the evaporation method, and the graphene oxide-iron composite film made by the suction filtration method can be used to obtain a more compact film.

In addition, as shown in curve (c) to curve (f) in Figure 6, the oxygen treated with deionized water Graphene oxide-iron composite film, graphene oxide-iron composite film treated with oxidant, graphene oxide-iron composite film treated with acid, and graphene oxide-iron composite film treated with alkali. Graphite diffraction angle (2θ) ) Are respectively 12.250 degrees, 11.726 degrees, 12.042 degrees and 12.312 degrees, showing that compared with the original graphene oxide-iron composite film, the graphene oxide-iron composite film treated with deionized water, and the graphene oxide treated with oxidant- The lattice constants of iron composite films, acid-treated graphene oxide-iron composite films, and alkali-treated graphene oxide-iron composite films are reduced.

Furthermore, as shown in Table 2, original graphene oxide-iron composite film, graphene oxide-iron composite film treated with deionized water, graphene oxide-iron composite film treated with oxidant, and graphite oxide treated with acid The interlayer spacing of the ene-iron composite film and the alkali-treated graphene oxide-iron composite film are 7.654Å, 7.217Å, 7.538Å, 7.18Å, and 7.341Å, respectively. It shows that due to deionized water, hydrogen peroxide solution, acid And lye through the compacting effect of the graphene oxide-iron composite film to make the graphene oxide-iron composite film treated with deionized water, the graphene oxide-iron composite film treated with oxidant, and the oxide treated with acid The layer spacing of the graphene-iron composite film and the alkali-treated graphene oxide-iron composite film is lower than that of the original graphene oxide-iron composite film.

[Example 5]

Using a syringe with a fixed height, the original graphene oxide-iron composite film Surfaces of graphene oxide-iron composite film treated with deionized water, graphene oxide-iron composite film treated with oxidant, graphene oxide-iron composite film treated with acid, and graphene oxide-iron composite film treated with alkali After tapping a drop of water, use the camera to take a side view, and then use the software to measure the contact angle between the water drop and the surface. The results show that the original graphene oxide-iron composite film, the graphene oxide-iron composite film treated with deionized water, the graphene oxide-iron composite film treated with an oxidant, the graphene oxide-iron composite film treated with an acid, and the The water contact angles of the alkali-treated graphene oxide-iron composite film were 49 degrees, 20 degrees, 79 degrees, 82 degrees and 81 degrees, respectively. The results show that compared with the original graphene oxide-iron composite film, the graphene oxide-iron composite film treated with deionized water has higher hydrophilicity, while the graphene oxide-iron composite film treated with oxidant has higher hydrophilicity. The treated graphene oxide-iron composite film and the alkali-treated graphene oxide-iron composite film have higher hydrophobicity.

[Example 6]

Soak the original graphene oxide film and the original graphene oxide-iron composite film in deionized water, acid solution (pH 1.2) and lye solution (pH 10.8) for 1 minute and 24 hours, respectively, and observe the original graphene oxide film and The structural integrity of the original graphene oxide-iron composite film. As shown in Figure 7, compared with the original graphene oxide film, the original graphene oxide-iron composite film is placed in deionized water, acid (pH 1.2) and lye (pH 10.8) for 24 hours. The graphene-iron composite film can still maintain a complete structure, showing that the original graphene oxide-iron composite film provides better structural stability.

[Example 7]

By filtration, 20 ml of 0.1 mM methyl blue solution was passed through the original graphene oxide-iron composite film, and the absorbance before filtration and the absorbance after filtration were detected by an ultraviolet-visible spectrometer (HACH DR6000) at a wavelength of 590 nm. Absorbance to calculate the efficiency of the original graphene oxide-iron composite film to remove methyl blue. As shown in Table 3 below, the removal rate of methyl blue in the first 10 ml of methyl blue solution was 82%, and the removal rate of methyl blue in the next 10 ml of methyl blue solution was 58%. The results show that the original graphene oxide-iron composite film can indeed effectively remove the methyl blue solution Inside the methyl blue.

[Example 8]

Use the original graphene oxide-iron composite membrane to filter the chlorpheniramine solution (pH 6.0) with a concentration of 100ppm for 1 hour, and detect the concentration of chlorpheniramine in the chlorpheniramine aqueous solution before and after filtration to calculate the original The efficiency of graphene oxide-iron composite film to remove chlorpheniramine. As shown in Table 4 below, the removal rate of chlorpheniramine in the first 10 ml of chlorpheniramine solution was 44.9%, and the removal rate of chlorpheniramine in the subsequent 41 ml to 50 ml of chlorpheniramine solution was 52.6%. The results show that the original graphene oxide-iron composite film can indeed effectively remove the chlorpheniramine in the chlorpheniramine solution through sieving.

The results of Examples 1 to 8 show that compared with graphene oxide-iron composite films, graphite oxide is obtained by mixing iron and graphene oxide aqueous solution in a specific proportion, and then through the steps of suction filtration and drying. The ene-iron composite film has a more compact and stable structure, and has high fluidity to water molecules. In addition, the graphene oxide-iron composite film prepared by the preparation method of the graphene oxide-iron composite film of the present invention can effectively remove nails through the adsorption characteristics of high surface area and the sieving characteristics of fine pores (about 10 Å). Methyl blue in the base blue solution or in the chlorpheniramine solution Chlorpheniramine. Therefore, the graphene oxide-iron composite film prepared by the method for preparing the graphene oxide-iron composite film of the present invention can be used in the solution for a long time, which improves the service life of the graphene oxide-iron composite film and achieves effective The effect of removing drugs or chemical pollutants in wastewater.

Although the present invention has been disclosed using the above-mentioned preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with the art without departing from the spirit and scope of the present invention may make various changes and modifications relative to the above-mentioned embodiments. The technical scope of the invention is protected. Therefore, the scope of protection of the invention shall be subject to the scope of the attached patent application.

S1: Steps to prepare graphene oxide aqueous solution

S2: Steps to obtain a mixed solution

S3: Steps to obtain a black film

S4: Steps to obtain graphene oxide-iron composite film

Claims (5)

A graphene oxide-iron composite film comprising a complete graphene oxide aqueous solution; mixing a ferrous ion salt with the graphene oxide aqueous solution, and the total iron ions in the ferrous ion salt and the graphene oxide aqueous solution The weight ratio of graphene oxide ranges from 1:4 to 1:8 to obtain a mixed solution; pour the mixed solution to an air extraction device for air extraction to remove moisture and obtain a black film; and The black film is prepared by the drying step. The graphene oxide-iron composite film includes a plurality of graphene oxide layers and iron ions. The functional groups on the surface of each graphene oxide layer include hydroxyl, epoxy, and carbonyl groups. And a carboxyl group, and the iron ion is combined with the hydroxyl group, the epoxy group, the carbonyl group and the oxygen on the carboxyl group, the graphene oxide-iron composite film has a water contact angle between 45 degrees and 55 degrees. According to the graphene oxide-iron composite film described in item 1 of the scope of patent application, the interlayer spacing of each graphene oxide-iron composite film is between 7 Å and 7.8 Å. According to the graphene oxide-iron composite film described in item 1 of the scope of patent application, the graphene oxide-iron composite film has a water contact angle of 49 degrees. A graphene oxide-iron composite film as described in the first scope of the patent application is used to remove pollutants in wastewater. The graphene oxide-iron composite film described in item 4 of the scope of patent application is used to remove pollutants in wastewater, where the pollutants include chlorpheniramine or methyl blue.

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