CN113069936A - Preparation method of large-flux graphene oxide filter membrane and application of large-flux graphene oxide filter membrane in ion screening - Google Patents
Preparation method of large-flux graphene oxide filter membrane and application of large-flux graphene oxide filter membrane in ion screening Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene oxide membrane with large flux, high interception and screening on high-valence metal ions, which comprises the following steps: and (3) swirling and ultrasonically treating 20-160 mL of 5-50 mg/L graphene oxide suspension, standing, and performing suction filtration to form a film to obtain the graphene oxide film. The preparation method of the invention has simple process, does not need complex process, does not need any methods such as physical, chemical and the like for crosslinking control, keeps the water environment infiltration state, and can be directly used for ion interception; the preparation method is easy to operate, so that the graphene oxide membrane has the effects of efficiently intercepting and screening metal high-valence ions, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry, and particularly relates to a preparation method of a graphene oxide film and application of the graphene oxide film.
Background
The graphene oxide membrane is theoretically considered to have excellent filter membrane characteristics of ultra-thin, high flow, energy conservation and the like, can be used as a next-generation filter membrane for filtering ions and molecules (Science 2011,333,712-717), and has long-term application prospects in the fields of seawater desalination, sewage treatment (Science2012,335, 442-444; Adv Funct Mater 2013,23,3693-3700), gas separation (Acs Nano 2016,10,3398-3409), biosensing (Nano Lett.2010,10,3163), proton conductors (Nano Lett.2008,8,2458; Nature 2014,516,227), lithium batteries (J Am Chem Soc 2012,134,8646-54) and super capacitors (Acs Nano2011,5,5463-547 1). Because the interlayer channel in the graphene oxide film is formed by stacking and self-assembling the interaction between the sheets, under the solution environment, water molecules rapidly permeate through the interlayer channel, so that the interaction between the sheets is weakened, and the interlayer channel is unstable; even permeation of water molecules within the membrane results in complete swelling of the graphene oxide membrane in solution. The unstable interlayer spacing and the swelling phenomenon cause the membrane to be easily damaged in an aqueous solution, and the retention performance of the membrane on metal ions in the aqueous solution is very difficult, so that the application of the graphene oxide membrane in the fields of ion screening and water treatment is greatly hindered.
Up to now, for the graphene oxide thin film, in order to stabilize the interlayer channel of the graphene oxide film, a method of partial reduction, chemical group cross-linking or physical confinement is mainly used to fix the interlayer distance and prevent the swelling phenomenon of the graphene oxide film in an aqueous solution. However, because the interlayer spacing in the membrane is fixed, the methods can only intercept a few ions with corresponding sizes, and have small application range on ion species; the ions of different sizes can not be intercepted simultaneously, and flexible and variable selective ion screening can not be realized. For example, chemical group cross-linking as used in the prior art increases the interlaminar channels (sciences 2014,343, 740-742; environ sci. technol.2013,47,3715-3723), the fixation of which makes the type of trapped ions very limited. More importantly, the methods not only have complex process and small applicable range of trapping ion species, but also can trap only a few metal ions after treatment, and simultaneously the water flux of the methods is less than 10Lm-2h- 1bar-1(Water flux of 2Lm for current commercial water purification film-2h-1bar-1) It is difficult to realize real industrial application.
Therefore, how to maintain the stability of the graphene oxide membrane and the layer channel, maintain high retention rate of metal cations commonly found in the environment, and have higher water flux is a problem to be solved urgently when the graphene oxide membrane is applied to seawater desalination and sewage purification.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the bottlenecks of small water flux and low interception efficiency caused by controlling channels in a graphene oxide membrane in the prior crosslinking technology; in the prior art, the size of a channel of a membrane after the control of an interlayer channel cannot be flexibly adjusted, so that the interception application range is small, and the effective screening of ions in a mixed ion solution cannot be realized; moreover, the existing crosslinking technology has complex process, and limits the practical industrial application. Currently, the graphene oxide membrane is used for intercepting the metal ion aqueous solution, and due to the fact that the actual water flux is small, the intercepting efficiency is low, and the interlayer distance control process is complex, the realization of industrial application still has great challenges. The invention aims to provide a high-flux (more than 75.0 Lm) for high-valence metal ions-2h-1bar-1) Methods for preparing graphene oxide membranes with high retention (greater than 99.5%) and sieving.
The second purpose of the invention is to provide an application of the graphene oxide film.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the present invention provides a method for preparing a graphene oxide membrane with large flux, high rejection and sieving for high valence metal ions, comprising the following steps: and (3) swirling and ultrasonically treating 20-160 mL of 5-50 mg/L graphene oxide suspension, standing, and performing suction filtration to form a film to obtain the graphene oxide film.
The graphene oxide film thickness can be controlled by the volume of the graphene oxide suspension. The graphene oxide suspension can be used in a volume of 20 mL-160 mL, and graphene oxide films with thicknesses of 50 nm-800 nm are detected from a Scanning Electron Microscope (SEM).
The thickness of the graphene oxide film is 50-800 nm, and preferably 100 nm.
The filtration membrane is formed by filtration with a microfiltration membrane of 0.1-0.22 μm as a substrate, preferably a microfiltration membrane of 0.22 μm.
The vacuum degree of the suction filtration membrane forming is 0.1-0.5 Mpa, but the vacuum filtration membrane forming is not limited to a suction filtration mode and the pressure value, and the membrane forming can be prepared under the conditions of pressure filtration and 0.1Mpa pressure.
After the graphene oxide is filtered into a wet membrane, the graphene oxide membrane which has large flux, high rejection rate and screening on the high-valence metal ion aqueous solution is obtained by utilizing the interaction of the high-valence metal ions and the graphene oxide lamella without any treatment.
The concentration of the graphene oxide suspension is 5 mg/L.
The graphene oxide suspension is prepared by a method conventional in the art, and preferably by an oxidation exfoliation graphite method (i.e., Hummers method).
The second aspect of the present invention provides an application of the graphene oxide membrane in screening and separating an aqueous solution of high valence metal ions.
The application comprises the following steps: and filtering the aqueous solution of the high-valence metal ions by using the graphene oxide membrane to realize the screening separation of the high-valence metal ions.
The high valence metal ion comprises cation and anion, the cation is divalent or above metal cation, preferably Cu2+、Pb2+、Zn2+、Cr2+、Mg2+、Ca2+、Fe3+Etc.; more preferably Cu2+、Pb2+、Zn2+、Cr2+、Fe3+(ii) a The anion is Cl-、F-、Br-、I-、OH-、SO4 2-、NO3 -Preferably Cl-、F-、Br-。
The concentration of the aqueous solution of the high valence metal ions is 1-1000 mg/L, preferably 50 mg/L.
The cation, when present in a mixture of a plurality of (two) ions, enables the sieving of a plurality of ions, e.g. containing Fe3+The mixed ion solution can realize the interception of Fe3+The purpose of permeating another ion.
The graphene oxide membrane realizes controllable interlayer spacing and oxygen control when screening and separating an aqueous solution of high-valence metal ionsThe size of the channel between layers of the graphene film is within
Within the range of
The amplitude is precisely controlled for dimensional changes.
In the aqueous solution of the high valence metal ions, the metal cations are Zn2+The interlayer channel size of the graphene oxide film with controllable interlayer spacing is
In the aqueous solution of the high valence metal ions, the metal cations are Cu2+The interlayer channel size of the graphene oxide film with controllable interlayer spacing is
In the aqueous solution of the high valence metal ions, the metal cation is Pb2+The interlayer channel size of the graphene oxide film with controllable interlayer spacing is
In the aqueous solution of the high valence metal ions, the metal cations are Fe3+The interlayer channel size of the graphene oxide film with controllable interlayer spacing is
The graphene oxide membrane has the effects of high flux and high retention rate on high-valence metal ions in an aqueous solution, and the main reason for retaining the high-valence metal ions is that due to the instability and the strong cation-pi effect of a hydration layer of the high-valence metal ions, the hydration layer is deformed and firmly adsorbed on the surface of an aromatic ring after the hydration layer enters a membrane channel. Therefore, not only the layer channel is controlled, but also the high valence metal ions are trapped.
The graphene oxide membrane is used for screening and separating high-valence metal ions in aqueous solution, such as Zn2++X，X＝Pb2 +、Cu2+、Cr2+、Mg2+、Ca2+、Fe3+The mixed solution has large flux and high efficiency screening function. The main reason why the higher valence metal ions can be sieved is due to Cu2+The relatively high valence metal ions of the hydrated layer of (A) are relatively small and unstable, and the stronger cation-pi effect, hydrated Cu2+After entering the membrane channel, the hydration layer is deformed and firmly adsorbed on the surface of the aromatic ring. Therefore, not only Cu2+The controlled layer channel is the smallest of the high valence ions, and retains Zn2+The ions can effectively intercept other high-valence ions.
The graphene oxide membrane is used for sieving and separating high-valence metal ions in aqueous solution, such as Fe3++X，X＝Pb2 +、Zn2+、Cr2+、Mg2+、Ca2+、Cu2+The mixed solution has large flux and high efficiency screening function. The main reason why the high valence metal ions can be sieved is due to Fe3+The relatively high valence metal ions of the hydrated layer of (A) are relatively large and unstable, and the stronger cation-pi action, hydrated Fe3+After entering the membrane channel, the hydration layer is deformed and firmly adsorbed on the surface of the aromatic ring. Therefore, not only Fe is trapped3+The ions themselves and the controlled layer channel are large, so that the rejection rate of other high-valence ions can be reduced, and the permeation screening of other ions is realized.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the invention provides a preparation method of a graphene oxide film capable of effectively screening mixed high-valence metal ions in an aqueous solution. The preparation method of the invention has simple process, does not need complex process, does not need any methods such as physical, chemical and the like for crosslinking control, keeps the water environment infiltration state, and can be directly used for ion interception; book (I)The preparation method is easy to operate, so that the graphene oxide membrane has the functions of efficiently intercepting and screening metal high-valence ions, and the water flux of the graphene oxide membrane can reach 75.2L m-2h-1bar-1The corresponding retention rate can reach 99.5 percent, and the method has good application prospect.
In the existing research of filtering ionic solution by a graphene oxide membrane, the limitation effect of the size of a water channel formed by a graphene oxide sheet layer on ions is mainly focused, but the strong ion-pi effect between the ions and an aromatic ring structure is ignored and has an important effect on the size of the membrane channel. The inventor finds that high-valence metal cations have strong cation-pi action on graphene oxide channels, and the size of a layer channel can be adaptively adjusted based on the strong interaction. This adaptive adjustment causes the hydrated layer of metal cations within the layer to deform, further limiting the penetration of the metal ions in solution. The applicant researches the control of various high-valence metal ions on the layer channel of the graphene oxide membrane, and finally realizes the cross-linking control without any physical, chemical and other methods after the graphene oxide suspension is prepared by suction filtration, so that the ion rejection rate is more than 99.5 percent and the water flux is more than 75.0Lm2h-1bar-1The invention relates to a breakthrough new method for intercepting high-valence metal ions by using graphene oxide, in particular to high-efficiency interception of high-valence metal ion aqueous solution.
The invention can realize that the ion retention rate is more than 99.5 percent and the water flux is more than 75.0Lm2h-1bar-1The high-efficiency interception of the high-valence metal ion aqueous solution is 20-40 times of the most economic nanofiltration membrane efficiency in the current market. The preparation method disclosed by the invention has universality on graphene oxide films prepared by various conventional methods.
The graphene oxide membrane provided by the invention does not need further process treatment, and can have large flux and high rejection rate for high-valence metal ions and can be used for sieving; the invention can realize the aim of FeCl3、CuSO4、Pb(NO3)2、ZnSO4Respectively has a water flux of 75.2L m-2h-1bar-1、56.6L m-2h-1bar-1、46.6L m-2h-1bar-1And 48.7L m-2h-1bar-1The corresponding retention rates were 99.5%, 97.8%, 86.9% and 83.0%, respectively. The water flux is one to two orders of magnitude larger than that of the reported graphene oxide membrane, is 20-40 times of the most economic nanofiltration membrane efficiency in the current market, and is better than 50L m-2h-1bar-1And the most excellent membrane reported with a retention of only 79%. The graphene oxide membrane is based on the strong ion-pi effect, realizes high-efficiency interception by adaptively adjusting the interlayer spacing corresponding to different ions, is simple in preparation process and easy to operate, has the functions of efficiently intercepting and screening metal high-valence ions, and has a good application prospect.
Drawings
Fig. 1 is a schematic flow chart of a process for preparing a graphene oxide film in example 1.
Fig. 2 shows the results of retention rate and water flux of the graphene oxide membrane on the aqueous solution of the metal ions in a high valence state in example 1.
FIG. 3 is a graph showing the retention efficiency of the graphene oxide membrane on the aqueous solution of high-valence metal ions in example 1, compared with the data in the prior art.
Fig. 4 shows the interlayer spacing of the graphene oxide membrane in example 1 during permeation of ions with different high valence states.
FIG. 5 shows the example 2 in which the graphene oxide film is first made of Fe3+The result schematic diagram of screening the mixed metal ions after controlling the graphene oxide film interlayer spacing; (a) is Fe3+Controlling the graphene oxide film interlayer spacing; (b) is made of Fe3+And controlling the retention rate of the mixed ions after the graphene oxide membrane interlamellar spacing.
FIG. 6 shows the pre-application of Zn to a graphene oxide film in example 32+The result schematic diagram of screening the mixed metal ions after controlling the graphene oxide film interlayer spacing; (a) for using Zn2+Controlling the retention rate of the graphene oxide membrane on mixed ions after interlayer spacing; (b) is Zn2+And controlling the interlayer distance of the graphene oxide film.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The graphene solution used in the present invention is prepared by an oxidation exfoliation graphite method (i.e., modified Hummers method), in which the graphene sheets suspended are monoatomic (about 0.5nm) thick and have a sheet size diameter of less than 1 μm. The improved Hummers method is a conventional method for preparing graphene oxide suspension, and can prepare a lamella with a lamella size of tens of nanometers to several micrometers.
Example 1
And (3) carrying out suction filtration on the graphene oxide suspension to form a membrane, and carrying out large-flux interception on high-valence metal ions in the aqueous solution.
The preparation method of the graphene oxide film comprises the following steps: swirling 40mL of graphene oxide suspension with the concentration of 5mg/L for 5 minutes, performing ultrasonic treatment for 1 hour, and standing overnight; taking a 0.22-micron microfiltration membrane as a substrate, and carrying out suction filtration on 40mL of suspension liquid in a vacuum pressure (0.1Mpa) by using a suction filtration device (1000 mL glass sand core suction filtration device under the brand name of Asia mai) to form a film; after film formation, the film is continuously filtered and cleaned by deionized water to remove impurities in the film, and the graphene oxide film (the film thickness is 100nm) is obtained.
The graphene oxide lamellae are monoatomic in thickness (about 0.5nm) and have a lamella size diameter of less than 1 μm. The graphene oxide suspension is prepared by oxidation stripping by a modified Hummers method.
And secondly, screening and separating the aqueous solution of the high-valence metal ions by using the graphene oxide membrane: CuSO with the concentration of 50mg/L4、Pb(NO3)2、ZnSO4、FeCl380mL of the aqueous solution is respectively filtered by adopting the graphene oxide membrane; recording the time when the volume of each 10mL of filtrate is measured, and converting the water flux; at a final volume of about 30mL, the filtrate was taken every 10mL and the ion concentration in the mother liquor and filtrate, respectively, was measured by ICP and the ion rejection calculated. The results show that the graphene oxide film pairs FeCl3、CuSO4、Pb(NO3)2、ZnSO4Respectively has a water flux of 75.2L m-2h-1bar-1、56.6L m-2h- 1bar-1、46.6L m-2h-1bar-1And 48.7L m-2h-1bar-1The corresponding retention rates were 99.5%, 97.8%, 86.9% and 83.0%, respectively. These water fluxes are one to two orders of magnitude greater than the reported water fluxes for graphene oxide membranes, and the reported water flux for the most heterogeneous permeable membranes is 50L m-2h-1bar-1And a retention of only 79% [ J.Mater.chem.A4(3),764-]。
And thirdly, after the interception experiment is finished, reserving the filtered wet membrane, carrying out XRD (X-ray diffraction) to detect the interlayer spacing, and analyzing the difference of water channels of the membrane after different high-valence ionic solutions permeate. Pure water and FeCl3、CuSO4、Pb(NO3)2、ZnSO4The interpolary distance of the graphene oxide membrane after permeation is respectively
And
from the results, it can be seen that the graphene oxide film has different interlayer distances during permeation of different high valence ions, and the difference between the layers is smaller than
The method shows that the high-valence ions and the interlayer spacing of the graphene oxide film have high-precision control.
Fig. 1 is a schematic flow chart of a process for preparing a graphene oxide film in example 1. Fig. 2 shows the results of retention rate and water flux of the graphene oxide membrane on the aqueous solution of the metal ions in a high valence state in example 1. The results show that the graphene oxide film is paired with FeCl3、CuSO4、Pb(NO3)2、ZnSO4Respectively has a water flux of 75.2L m-2h-1bar-1、56.6L m-2h-1bar-1、46.6L m-2h-1bar-1And 48.7L m-2h-1bar-1The corresponding retention rates were 99.5%, 97.8%, 86.9% and 83.0%, respectively.
FIG. 3 is a graph showing the retention efficiency of the graphene oxide membrane on the aqueous solution of high-valence metal ions in example 1, compared with the data in the prior art. The water flux of the graphene oxide membrane of the present invention is one to two orders of magnitude greater than that reported for graphene oxide membranes, and the water flux reported for the most heterogeneous permeable membrane is 50L m-2h-1bar-1And a retention of only 79% [ J.Mater.chem.A4(3),764-]。
Fig. 4 shows the interlayer spacing of the graphene oxide membrane in example 1 during permeation of ions with different high valence states. Pure water and FeCl3、CuSO4、Pb(NO3)2、ZnSO4The interpolary distance of the graphene oxide membrane after permeation is respectively
And
from the results, it can be seen that the graphene oxide film has different interlayer distances during permeation of different high valence ions, and the difference between the layers is smaller than
The method shows that the high-valence ions and the interlayer spacing of the graphene oxide film have high-precision control. The graphene oxide membrane prepared by the embodiment has excellent filter membrane characteristics of large flux, high rejection rate, simple preparation process, energy conservation and the like, and can be directly used for screening and separating high-valence ion aqueous solution.
Example 2
Filtering the graphene oxide suspension to form a film, and using Fe3+Control of interlayer spacing and for aqueous solutionsThe high-flux screening is carried out on various mixed high-valence metal ions:
the preparation method of the graphene oxide film comprises the following steps: swirling 40mL of graphene oxide suspension with the concentration of 5mg/L for 5 minutes, performing ultrasonic treatment for 1 hour, and standing overnight; taking a 0.22-micron microfiltration membrane as a substrate, and carrying out suction filtration on 40mL of suspension liquid in a vacuum pressure (0.1Mpa) by using a suction filtration device (1000 mL glass sand core suction filtration device under the brand name of Asia mai) to form a film; and after film formation, continuously performing suction filtration and cleaning by using deionized water to remove impurities in the film, thereby obtaining the graphene oxide film.
The graphene oxide lamellae are monoatomic in thickness (about 0.5nm) and have a lamella size diameter of less than 1 μm. The graphene oxide suspension is prepared by oxidation stripping by a modified Hummers method.
And secondly, screening and separating the aqueous solution of the high-valence metal ions by using the graphene oxide membrane:
Fe3+ion control layer spacing: FeCl with the concentration of 50mg/L3Was filtered using the above-described graphene oxide membrane (according to the method of the second step in example 1) to control the interlayer distance in the graphene oxide membrane.
Screening of mixed ions: 80mL of mixed salt solution containing FeCl with the concentration of 50mg/L3And another salt solution (CuSO) at a concentration of 50mg/L4、Pb(NO3)2Or ZnSO4One of (1), the volume ratio is 1:1 (namely 40mL each), the filtration is carried out continuously under the atmospheric pressure vacuum (0.1MPa) for screening, the time of every 10mL of filtrate volume is recorded, and the water flux is converted; at a final volume of about 30mL, the filtrate was taken every 10mL and the ion concentration in the mother liquor and filtrate, respectively, was measured by ICP and the ion rejection calculated. The results show that Fe3+Controlled graphene oxide film pair of Pb (NO)3)2、CuSO4、ZnSO4The retention rate of the aqueous solution is only 47.6%, 39.8% and 24.8%, and the corresponding water flux is 61.9L m-2h-1bar-1、42.9L m-2h-1bar-1And 44.7L m-2h-1bar-1. Indicates Fe3+After control, due toGreater interlayer spacing for Pb (NO)3)2、CuSO4、ZnSO4The rejection rate of the aqueous solution decreases and the permeation of these ions is achieved.
And thirdly, after the interception experiment is finished, reserving the filtered wet membrane, carrying out XRD (X-ray diffraction) to detect the interlayer spacing, and analyzing the difference of water channels of the membrane after different high-valence ionic solutions permeate. From the results, FeCl3After control, the catalyst contains CuSO4、Pb(NO3)2、ZnSO4The mixed salt solution permeates the interlayer spaces
Indicating FeCl3The controlled graphene oxide film was very stable in interlayer spacing, with larger interlayer spacing leading to rapid permeation of other ions, indicating that FeCl controlled by selection of larger spacing3Can realize CuSO4、Pb(NO3)2、ZnSO4Entrapment and control of sieving.
FIG. 5 shows the example 2 in which the graphene oxide film is first made of Fe3+The result schematic diagram of screening the mixed metal ions after controlling the graphene oxide film interlayer spacing; (a) is Fe3+Controlling the graphene oxide film interlayer spacing; (b) is made of Fe3+And controlling the retention rate of the mixed ions after the graphene oxide membrane interlamellar spacing. FeCl3After control, the catalyst contains CuSO4、Pb(NO3)2、ZnSO4The mixed salt solution permeates the interlayer spaces
Indicating FeCl3The controlled interlayer spacing of the graphene oxide film is very stable.
With Fe3+After control of graphene oxide film, for Fe3+、Pb2+、Cr2+Trapping, to Cu2+、Zn2+The filterable high flux, high screening efficiency, simple preparation process, energy conservation and other excellent filter membrane characteristics can be directly used for screening and separating high-valence ionic water solution.
Example 3
Filtering the graphene oxide suspension to form a film, and using Zn2+Controlling the interlayer spacing, and carrying out large-flux screening on various mixed high-valence metal ions in the aqueous solution:
the preparation method of the graphene oxide film comprises the following steps: swirling 40mL of graphene oxide suspension with the concentration of 5mg/L for 5 minutes, performing ultrasonic treatment for 1 hour, and standing overnight; taking a 0.22-micron microfiltration membrane as a substrate, and carrying out vacuum filtration on 40mL of suspension liquid at an air pressure (0.1Mpa) by using a filtration device (1000 mL glass sand core filtration device of Simi brand); and after film formation, continuously performing suction filtration and cleaning by using deionized water to remove impurities in the film, thereby obtaining the graphene oxide film.
The graphene oxide lamellae are monoatomic in thickness (about 0.5nm) and have a lamella size diameter of less than 1 μm. The graphene oxide suspension is prepared by oxidation stripping by a modified Hummers method.
And secondly, screening and separating the aqueous solution of the high-valence metal ions by using the graphene oxide membrane:
Zn2+ion control layer spacing: ZnSO with a concentration of 50mg/L420mL of the solution was filtered using the above-described graphene oxide membrane (according to the method of the second step in example 1) to control the interlayer spacing within the graphene oxide membrane.
Screening of mixed ions: 80mL of mixed salt solution containing ZnSO with the concentration of 50mg/L4And another salt solution (CuSO) at a concentration of 50mg/L4、Pb(NO3)2Or FeCl3One of the above), the volume ratio is 1:1 (namely 40mL each), and the vacuum filtration is continuously carried out under one atmospheric pressure (0.1MPa) for screening; recording the time when the volume of each 10mL of filtrate is measured, and converting the water flux; at a final volume of about 30mL, the filtrate was taken every 10mL and the ion concentration in the mother liquor and filtrate, respectively, was measured by ICP and the ion rejection calculated. The results show that Zn2+Controlled graphene oxide film pair FeCl3、Pb(NO3)2、CuSO4The retention rates of the aqueous solutions were 99.6%, 95.1% and 92.6%, corresponding to a water flux of 44.2L m, respectively-2h-1bar-1、42.9L m-2h-1bar-1And 24.2L m-2h-1bar-1. Indicates Zn2+After control, due to smaller layer spacing, for FeCl3、Pb(NO3)2、CuSO4The retention rate of the aqueous solution is improved, and the effective retention of the ions is realized.
And thirdly, after the interception experiment is finished, reserving the filtered wet membrane, carrying out XRD (X-ray diffraction) to detect the interlayer spacing, and analyzing the difference of water channels of the membrane after different high-valence ionic solutions permeate. From the results, ZnSO4After control, for the FeCl containing pairs3、Pb(NO3)2、CuSO4The mixed salt solution permeates the interlayer spaces
Indicating ZnSO4The interlayer spacing of the controlled graphene oxide film is very stable, and the smaller interlayer spacing leads to effective interception of other ions, which shows that the ZnSO controlled by the smaller spacing is selected4Can realize FeCl3、Pb(NO3)2、CuSO4Entrapment and control of sieving.
FIG. 6 shows the pre-application of Zn to a graphene oxide film in example 32+The result schematic diagram of screening the mixed metal ions after controlling the graphene oxide film interlayer spacing; (a) for using Zn2+Controlling the retention rate of the graphene oxide membrane on mixed ions after interlayer spacing; (b) is Zn2+And controlling the interlayer distance of the graphene oxide film. From the results, ZnSO4After control, for the FeCl-containing solution3、Pb(NO3)2、CuSO4The mixed salt solution permeates the interlayer spaces
Indicating ZnSO4The controlled interlayer spacing of the graphene oxide film is very stable. With Zn2+After control of graphene oxide film, for Fe3+、Pb2+、Cu2+The high-flux filtration membrane has the excellent filtration membrane characteristics of high flux interception, high screening efficiency, simple preparation process, energy conservation and the like, and can be directly used for screening and separating high-valence ionic water solution.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing a graphene oxide film, comprising the steps of:
and (3) swirling and ultrasonically treating 20-160 mL of 5-50 mg/L graphene oxide suspension, standing, and performing suction filtration to form a film to obtain the graphene oxide film.
2. The method for producing a graphene oxide film according to claim 1, wherein the graphene oxide film has a thickness of 50 to 800 nm.
3. The method for preparing the graphene oxide film according to claim 1, wherein the filtration film is formed by filtration using a microfiltration membrane of 0.1-0.22 μm as a substrate.
4. The method for preparing the graphene oxide film according to claim 1, wherein the vacuum degree of the film formed by suction filtration is 0.1-0.5 Mpa.
5. Use of a graphene oxide membrane prepared by the method of any one of claims 1 to 4 for sieving and separating an aqueous solution of a metal ion in a high valence state.
6. The use of the graphene oxide membrane according to claim 5 for sieving and separating an aqueous solution of a metal ion in a high valence state, wherein the use comprises the steps of: and filtering the aqueous solution of the high-valence metal ions by using the graphene oxide membrane to realize the screening separation of the high-valence metal ions.
7. The use of the graphene oxide membrane according to claim 5 for sieving and separating an aqueous solution of metal ions in a high valence state, wherein the metal ions in a high valence state comprise cations and anions, and the cations are divalent and higher metal cations.
8. The use of the graphene oxide membrane according to claim 7 for sieving and separating an aqueous solution of a metal ion in a high valence state, wherein the cation is Cu2+、Pb2+、Zn2+、Cr2+、Mg2+、Ca2+、Fe3+At least one of (1).
9. The use of the graphene oxide membrane according to claim 7 for sieving and separating an aqueous solution of a metal ion in a high valence state, wherein the anion is Cl-、F-、Br-、I-、OH-、SO4 2-、NO3 -At least one of (1).
10. The use of the graphene oxide membrane for sieving and separating an aqueous solution of metal ions in a high valence state according to claim 5, wherein the graphene oxide membrane realizes controllable interlayer spacing when sieving and separating an aqueous solution of metal ions in a high valence state, and the size of the interlayer channel of the graphene oxide membrane is within the range of
Within the range.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113559722A (en) * | 2021-08-17 | 2021-10-29 | 北京理工大学 | Defect-rich water-stable graphene oxide film and preparation method and application thereof |
| CN114288867A (en) * | 2021-11-18 | 2022-04-08 | 兰州大学 | Preparation method of vortex graphene oxide water purification film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028111A (en) * | 2013-03-08 | 2014-09-10 | 北京师范大学 | Method for preparing sandwich graphene oxide separation membrane |
| US20180036690A1 (en) * | 2016-08-04 | 2018-02-08 | King Fahd University Of Petroleum And Minerals | Method for preparing a polygraphene membrane |
-
2020
- 2020-01-03 CN CN202010003915.3A patent/CN113069936A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028111A (en) * | 2013-03-08 | 2014-09-10 | 北京师范大学 | Method for preparing sandwich graphene oxide separation membrane |
| US20180036690A1 (en) * | 2016-08-04 | 2018-02-08 | King Fahd University Of Petroleum And Minerals | Method for preparing a polygraphene membrane |
Non-Patent Citations (1)
| Title |
|---|
| 陈亮: "基于离子控制的氧化石墨烯膜的水处理", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113559722A (en) * | 2021-08-17 | 2021-10-29 | 北京理工大学 | Defect-rich water-stable graphene oxide film and preparation method and application thereof |
| CN113559722B (en) * | 2021-08-17 | 2022-03-22 | 北京理工大学 | Defect-rich water-stable graphene oxide film and preparation method and application thereof |
| CN114288867A (en) * | 2021-11-18 | 2022-04-08 | 兰州大学 | Preparation method of vortex graphene oxide water purification film |
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