CN109772183A - A kind of anionic compound intercalation g-C3N4The preparation method and applications of composite membrane - Google Patents
A kind of anionic compound intercalation g-C3N4The preparation method and applications of composite membrane Download PDFInfo
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Abstract
The invention discloses a kind of anionic compound intercalation g-C3N4The preparation method and applications of composite membrane obtain body phase g-C by thermal polymerization method first3N4；It removes to obtain g-C using physics3N4Nanometer sheet dispersion liquid；Finally by anionic compound and g-C3N4Nanometer sheet dispersion liquid mixed deposit arrives anionic compound intercalation g-C on perforated substrate film3N4Composite membrane.Compared with prior art, anionic compound intercalation g-C prepared by the present invention3N4Composite membrane has higher water flux and superior selectivity.
Description
Technical field
The present invention relates to the preparation methods of two-dimensional films, and in particular to a kind of anionic compound intercalation g-C3N4Composite membrane
Preparation method and applications.
Background technique
With the rapid development of economy, environmental pollution and shortage of resources problem are increasingly protruded.Various trade effluents and life
The discharge carelessly of sewage living, increases more heavy burden with regard to the country of shortage of resources to script.Membrane separation technique is due to its letter
The advantages that single process and low energy consumption and be widely used in wastewater treatment.In recent years, graphene oxide, transition metal two
The two-dimensional materials such as sulfide, covalent organic compound, metallo-organic compound, layered double-hydroxide due to its possess it is monatomic
The advantages that thickness, hole or non-porous structure, stable chemical property and thermal stability and become two-dimensional films preparation substrate.But
Existing two-dimensional films still have shortcoming, such as graphene oxide two-dimensional film, and preparation method is cumbersome, and are easy to be swollen in water.
" membrane science and technology magazine " (Journal of Membrane Science, 2015,490,72-83) is reported
It is a kind of by g-C3N4Nanometer sheet mixes in polymer substrate, prepares highly selective hybridized film.By by a certain amount of g-C3N4Nanometer
Piece powder is distributed in water and is ultrasonically treated, and sodium alginate (SA) is then dissolved in 30 DEG C of stirring 5h in above-mentioned dispersion.It will
Film liquid is spun on basilar memebrane polyacrylonitrile (PAN), then in 0.5mol/LCaCl2Aqueous solution submergence 10min hands over it with film
Connection, and be rinsed with water and remove uncrosslinked CaCl2.Although the hybridized film flux of preparation and selective purer SA film have certain
It is promoted, but complex process, film poor controllability are unfavorable for mass production.
Chinese patent CN105214512 discloses a kind of preparation method of carrier surface graphene oxide membrane, and this method is first
Amino active group first is introduced in carrier surface, graphene oxide uniform load is then obtained into graphene oxide to carrier surface
Film.Although the preparation method enhances the active force between carrier and graphene oxide membrane, improve the retention to dye molecule
Rate, but cross-film resistance is also increased, cause flux there was only 5Lh-1·m-2·bar-1, and complex process.
Summary of the invention
The present invention is in view of the above shortcomings of the prior art, it is desirable to provide a kind of anionic compound intercalation g-C3N4Composite membrane
Preparation method and applications.Composite membrane of the present invention has higher water flux and superior selectivity.
Anionic compound intercalation g-C of the present invention3N4The preparation method of composite membrane, obtains body by thermal polymerization method first
Phase g-C3N4；It removes to obtain g-C using physics3N4Nanometer sheet dispersion liquid；Finally by anionic compound and g-C3N4Nanometer sheet
Dispersion liquid mixed deposit arrives anionic compound intercalation g-C on perforated substrate film3N4Composite membrane.
Anionic compound intercalation g-C of the present invention3N4The preparation method of composite membrane, specifically comprises the following steps:
Step 1: the melamine or urea for weighing 1-5g, which are placed in mortar, grinds 10-20min, is subsequently placed in Muffle furnace
8-12h is calcined at 500-600 DEG C, obtains body phase g-C3N4；
Step 2: the body phase g-C that step 1 is obtained3N4Grind into powder is configured to g-C3N4Suspension, heating ultrasound, so
20min is centrifuged under 8000rpm afterwards, centrifugation leaves and takes supernatant three times, obtains the g-C of stable dispersion3N4Nanometer sheet dispersion liquid；
Step 3: the g-C that step 2 obtains3N4Nanometer sheet dispersion liquid and the mixing of anionic compound solution, heat ultrasound 10-
20min is uniformly mixed it, and pretreated perforated substrate film is loaded mixing film liquid to get yin by nanometer sheet package technique
Ionic compound intercalation g-C3N4Composite membrane, drying removal excess of solvent.
In step 2, g-C3N4The concentration of suspension is 3-6mg/mL；The temperature of heating ultrasound is 80-120 DEG C, ultrasonic time
For 10-18h.
In step 3, the anionic compound solution be sulfonated poly (phenylene oxide) (SPPO) solution, azovan blue (EB) solution or
Methyl blue (MB) solution, the concentration of the anionic compound solution are 1mg/mL.
In step 3, g-C3N4The mass ratio of nanometer sheet dispersion liquid and anionic compound solution is 1:0.5-1:10.
In step 3, the perforated substrate film includes poly (ether sulfone) film, polyvinylidene fluoride film, polycarbonate membrane, anodised aluminium
One of film, polyacrylonitrile film etc., and the aperture of porous carrier is 100-450nm.The pretreatment of perforated substrate film refer to by
Perforated substrate film, which is placed in deionized water, to be impregnated 1-3 days, and pretreated perforated substrate film is obtained.
In step 3, the nanometer sheet package technique includes vacuum filtration, LBL self-assembly, electrostatic spinning, spin coating etc..
In step 3, the drying is in 40-80 DEG C of dry 8-15h.
Anionic compound intercalation g-C prepared by the present invention3N4Composite membrane with a thickness of 200nm-1 μm.
In anionic compound, the structural formula of sulfonated poly (phenylene oxide) (SPPO) is as follows:
In anionic compound, the structural formula of azovan blue (EB) is as follows:
In anionic compound, the structural formula of methyl blue (MB) is as follows:
Anionic compound intercalation g-C prepared by the present invention3N4Application of the composite membrane in nanofiltration is that the present invention is compound
Film is fixed in nanofiltration device, for retaining size and electrically charged different nanoparticle.
The nanoparticle includes methylene blue, methyl blue, rhodamine B, azovan blue, methyl orange, Congo red etc..
The principle of the present invention are as follows: g-C3N4It is a kind of structure similar to graphene, but the g-C in water environment3N4Film
Interlamellar spacing is able to maintain constant, and g-C3N4Natural triangular nano pore structure and fault of construction make it more than graphene oxide
One molecule transport approach.Nevertheless, leading to water flux not since interlamellar spacing and aperture size all only have 0.3nm or so
It is high.The present invention passes through in g-C3N4Intercalation various sizes of anionic compound increases the interlamellar spacing of film to reach between nanometer sheet
The purpose of water flux is improved, while being able to maintain high rejection again.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1, the present invention is using anionic compound (SPPO, EB, MB) and two dimension g-C3N4The method that nanometer sheet homogeneously assembles,
It is prepared for a kind of novel porous anionic compound intercalation g-C3N4Composite film material.With " membrane science and technology magazine "
The SA/g-C of (Journal of Membrane Science, 2015,490,72-83) report3N4Compound membrane preparation method is compared,
Raw material is cheap, and simple process, reaction condition is easily-controllable, is easy to be mass produced.
2, the yin compared with a kind of preparation method of the Chinese patent CN105214512 carrier surface graphene oxide membrane announced
Ionic compound intercalation g-C3N4Composite membrane simple process, chemical property and stable mechanical performance, due to its stable interlayer knot
Structure, water flux can increase by 500 times in nanofiltration application, while rejection is also able to maintain 90% or so numerical value.
Detailed description of the invention
Fig. 1 is embodiment 1g-C3N4Atomic force microscope (AFM) figure of two-dimensional nano piece.
Fig. 2 is embodiment 2SPPO/g-C3N4Scanning electron microscope (SEM) figure of composite film surface.
Fig. 3 is embodiment 2SPPO/g-C3N4Scanning electron microscope (SEM) figure of composite membrane section.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1:
1, the melamine for weighing 1g, which is placed in mortar, grinds 10min, is placed in 500 DEG C of calcinings, calcination time in Muffle furnace
For 8h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 3mg/mL g-C3N4It is super to carry out 80 DEG C of heating for suspension
Sound 10h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.08mg/mL.
3, anionic compound sulfonated poly (phenylene oxide) (SPPO) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and SPPO solution 1:1 in mass ratio mixing, heating ultrasound 10min make its mixing
Uniformly, Kynoar (PVDF) substrate for being 0.22 μm by the aperture impregnated with deionized water 1 day by vacuum filtration method
Film load mixing film liquid is to get SPPO/g-C3N4Composite membrane.40 DEG C of drying 8h remove excess of solvent.
G-C obtained in the present embodiment step 23N4Nanometer sheet carries out the test of atomic force microscope (AFM), such as Fig. 1 institute
Show, as can be seen from the figure the thickness of nanometer sheet about 1nm, about 1.5 μm of size, shows with monoatomic thickness.
5, the SPPO/g-C of the present embodiment3N4Application of the composite membrane in nanofiltration: by the above-mentioned SPPO/g- for being carried on PVDF
C3N4Composite membrane is fixed in filter device, and concentration is positively charged MLB (methylene blue) aqueous solution of 15 μm of ol/L, water flux
3245L·h-1·m-2·bar-1, the rejection to methylene blue is 100%；Concentration is the electronegative MB (methyl of 50 μm of ol/L
It is blue) aqueous solution, water flux 2783Lh-1·m-2·bar-1, the rejection to methyl blue is 100%.
Embodiment 2:
1, the melamine for weighing 1g, which is placed in mortar, grinds 10min, is placed in 510 DEG C of calcinings, calcination time in Muffle furnace
For 9h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 3mg/mL g-C3N4It is super to carry out 80 DEG C of heating for suspension
Sound 10h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.08mg/mL.
3, anionic compound sulfonated poly (phenylene oxide) (SPPO) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and SPPO solution 1:1 in mass ratio mixing, heating ultrasound 15min make its mixing
Uniformly, Kynoar (PVDF) substrate for being 0.22 μm by the aperture impregnated with deionized water 1 day by vacuum filtration method
Film load mixing film liquid is to get SPPO/g-C3N4Composite membrane.40 DEG C of drying 8h remove excess of solvent.
The present embodiment step 4 SPPO/g-C obtained3N4Composite membrane is scanned the test of Electronic Speculum (SEM), composite membrane
Surface and section are as shown in Figure 2 and Figure 3, it can be seen from the figure that film surface smoother and no defect, the thickness of film is about
250nm。
5, the SPPO/g-C of the present embodiment3N4Application in nanofiltration: by the above-mentioned SPPO/g-C for being carried on PVDF3N4It is multiple
It closes film to be fixed in filter device, concentration is positively charged RB (rhodamine B) aqueous solution of 10 μm of ol/L, water flux 1638L
h-1·m-2·bar-1, the rejection of rhodamine B is 94.9%.
Embodiment 3:
1, the melamine for weighing 2g, which is placed in mortar, grinds 15min, is placed in 510 DEG C of calcinings, calcination time in Muffle furnace
For 9h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 4mg/mL g-C3N4It is super to carry out 90 DEG C of heating for suspension
Sound 12h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.10mg/mL.
3, anionic compound sulfonated poly (phenylene oxide) (SPPO) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and SPPO solution 1:5 in mass ratio mixing, heating ultrasound 15min make its mixing
Uniformly, Kynoar (PVDF) substrate for being 0.22 μm by the aperture impregnated with deionized water 2 days by vacuum filtration method
Film load mixing film liquid is to get SPPO/g-C3N4Composite membrane.60 DEG C of drying 10h remove excess of solvent.
5, the SPPO/g-C of the present embodiment3N4Application in nanofiltration: by the above-mentioned SPPO/g-C for being carried on PVDF3N4It is multiple
It closes film to be fixed in filter device, concentration is positively charged MLB (methylene blue) aqueous solution of 15 μm of ol/L, water flux
2481L·h-1·m-2·bar-1, the rejection to methylene blue is 98.9%；Concentration is the electronegative MB (methyl of 50 μm of ol/L
It is blue) aqueous solution, water flux 2791Lh-1·m-2·bar-1, the rejection to methyl blue is 100%.
Embodiment 4:
1, the melamine for weighing 3g, which is placed in mortar, grinds 20min, is placed in 530 DEG C of calcinings, calcination time in Muffle furnace
For 9h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 6mg/mL g-C3N4It is super to carry out 100 DEG C of heating for suspension
Sound 14h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.25mg/mL.
3, anionic compound sulfonated poly (phenylene oxide) (SPPO) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and SPPO solution 1:10 in mass ratio mixing, heating ultrasound 20min make its mixing
Uniformly, Kynoar (PVDF) substrate for being 0.22 μm by the aperture impregnated with deionized water 3 days by vacuum filtration method
Film load mixing film liquid is to get SPPO/g-C3N4Composite membrane.80 DEG C of drying 10h remove excess of solvent.
5, the SPPO/g-C of the present embodiment3N4Application in nanofiltration: by the above-mentioned SPPO/g-C for being carried on PVDF3N4It is multiple
It closes film to be fixed in filter device, concentration is positively charged MLB (methylene blue) aqueous solution of 15 μm of ol/L, water flux
1701L·h-1·m-2·bar-1, the rejection to methylene blue is 95.5%；Concentration is the electronegative EB (Yi Wen of 10 μm of ol/L
This is blue) aqueous solution, water flux 716Lh-1·m-2·bar-1, the rejection of azovan blue is 100%.
Embodiment 5:
1, the melamine for weighing 5g, which is placed in mortar, grinds 20min, is placed in 550 DEG C of calcinings, calcination time in Muffle furnace
For 10h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 6mg/mL g-C3N4It is super to carry out 90 DEG C of heating for suspension
Sound 12h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.15mg/mL.
3, anionic compound azovan blue (EB) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and EB solution 1:0.5 in mass ratio mixing, heating ultrasound 20min make its mixing
Uniformly, Kynoar (PVDF) substrate for being 0.22 μm by the aperture impregnated with deionized water 3 days by vacuum filtration method
Film load mixing film liquid is to get EB/g-C3N4Composite membrane.60 DEG C of drying 12h remove excess of solvent.
5, the EB/g-C of the present embodiment3N4Application of the composite membrane in nanofiltration: by the above-mentioned EB/g-C for being carried on PVDF3N4
Composite membrane is fixed in filter device, and concentration is positively charged RB (rhodamine B) aqueous solution of 10 μm of ol/L, water flux
1081L·h-1·m-2·bar-1, the rejection of rhodamine B is 91.5%；Concentration is 50 μm of electronegative MB of ol/L (methyl blue)
Aqueous solution, water flux 1670Lh-1·m-2·bar-1, the rejection of methyl blue is 88.0%.
Embodiment 6:
1, the melamine for weighing 5g, which is placed in mortar, grinds 20min, is placed in 550 DEG C of calcinings, calcination time in Muffle furnace
For 11h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 6mg/mL g-C3N4It is super to carry out 100 DEG C of heating for suspension
Sound 18h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.40mg/mL.
3, anionic compound azovan blue (EB) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and EB solution 1:1 in mass ratio mixing, heating ultrasound 20min keep its mixing equal
Kynoar (PVDF) basilar memebrane that is even, being 0.22 μm by the aperture impregnated with deionized water 3 days by vacuum filtration method
Load mixing film liquid is to get EB/g-C3N4Composite membrane.60 DEG C of drying 12h remove excess of solvent.
5, the EB/g-C of the present embodiment3N4Application of the composite membrane in nanofiltration: by the above-mentioned EB/g-C for being carried on PVDF3N4
Composite membrane is fixed in filter device, and concentration is 50 μm of ol/L electronegative MB (methyl blue) aqueous solutions, water flux 1908L
h-1·m-2·bar-1, the rejection of methyl blue is 91.2%；Concentration is that the positively charged MLB (methylene blue) of 15 μm of ol/L is water-soluble
Liquid, water flux 1988Lh-1·m-2·bar-1, the rejection to methylene blue is 98%.
Embodiment 7:
1, the melamine for weighing 5g, which is placed in mortar, grinds 20min, is placed in 550 DEG C of calcinings, calcination time in Muffle furnace
For 12h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 6mg/mL g-C3N4It is super to carry out 100 DEG C of heating for suspension
Sound 18h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.40mg/mL.
3, anionic compound azovan blue (EB) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and EB solution 1:5 in mass ratio mixing, heating ultrasound 20min keep its mixing equal
Kynoar (PVDF) basilar memebrane that is even, being 0.22 μm by the aperture impregnated with deionized water 3 days by vacuum filtration method
Load mixing film liquid is to get EB/g-C3N4Composite membrane.60 DEG C of drying 12h remove excess of solvent.
5, the EB/g-C of the present embodiment3N4Application of the composite membrane in nanofiltration: by the above-mentioned EB/g-C for being carried on PVDF3N4
Composite membrane is fixed in filter device, and concentration is 50 μm of ol/L electronegative MB (methyl blue) aqueous solutions, water flux 2767L
h-1·m-2·bar-1, the rejection of methyl blue is 100%；Concentration is that the positively charged MLB (methylene blue) of 15 μm of ol/L is water-soluble
Liquid, water flux 1463Lh-1·m-2·bar-1, the rejection to methylene blue is 99.0%.
Embodiment 8:
1, the melamine for weighing 5g, which is placed in mortar, grinds 20min, is placed in 550 DEG C of calcinings, calcination time in Muffle furnace
For 10h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 6mg/mL g-C3N4It is super to carry out 100 DEG C of heating for suspension
Sound 18h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.40mg/mL.
3, anionic compound methyl blue (MB) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and MB solution 1:0.5 in mass ratio mixing, heating ultrasound 20min make its mixing
Uniformly, Kynoar (PVDF) substrate for being 0.22 μm by the aperture impregnated with deionized water 3 days by vacuum filtration method
Film load mixing film liquid is to get MB/g-C3N4Composite membrane.60 DEG C of drying 12h remove excess of solvent.
5, the MB/g-C of the present embodiment3N4Application of the composite membrane in nanofiltration: by the above-mentioned MB/g-C for being carried on PVDF3N4
Composite membrane is fixed in filter device, and concentration is 10 μm of ol/L electronegative EB (azovan blue) aqueous solutions, water flux
2545L·h-1·m-2·bar-1, the rejection of azovan blue is 98.0%；Concentration is the positively charged MLB (methylene of 15 μm of ol/L
Base is blue) aqueous solution, water flux 1280Lh-1·m-2·bar-1, the rejection to methylene blue is 98.0%.
Embodiment 9:
1, the melamine for weighing 5g, which is placed in mortar, grinds 20min, is placed in 550 DEG C of calcinings, calcination time in Muffle furnace
For 10h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 6mg/mL g-C3N4It is super to carry out 100 DEG C of heating for suspension
Sound 18h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.40mg/mL.
3, anionic compound methyl blue (MB) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and MB solution 1:1 in mass ratio mixing, heating ultrasound 20min keep its mixing equal
Kynoar (PVDF) basilar memebrane that is even, being 0.22 μm by the aperture impregnated with deionized water 3 days by vacuum filtration method
Load mixing film liquid is to get MB/g-C3N4Composite membrane.60 DEG C of drying 12h remove excess of solvent.
5, the MB/g-C of the present embodiment3N4Application of the composite membrane in nanofiltration: by the above-mentioned MB/g-C for being carried on PVDF3N4
Composite membrane is fixed in filter device, and concentration is 10 μm of ol/L electronegative EB (azovan blue) aqueous solutions, water flux
2226L·h-1·m-2·bar-1, the rejection of azovan blue is 98.1%；Concentration is the electronegative MB (methyl of 50 μm of ol/L
It is blue) aqueous solution, water flux 1757Lh-1·m-2·bar-1, the rejection of methyl blue is 100%.
Embodiment 10:
1, the melamine for weighing 5g, which is placed in mortar, grinds 20min, is placed in 550 DEG C of calcinings, calcination time in Muffle furnace
For 10h, body phase g-C is obtained3N4。
2, the body phase g-C that will be obtained3N4Grind into powder is made into 6mg/mL g-C3N4It is super to carry out 100 DEG C of heating for suspension
Sound 18h, then 8000rpm, are centrifuged 20min, and centrifugation takes supernatant three times, obtains stable dispersion g-C3N4Nanometer sheet dispersion liquid.With purple
The concentration that outside-visible spectrophotometer measures nanometer sheet is 0.40mg/mL.
3, anionic compound methyl blue (MB) is made into concentration is 1mg/mL.
4, by g-C3N4Nanometer sheet dispersion liquid and MB solution 1:5 in mass ratio mixing, heating ultrasound 20min keep its mixing equal
Kynoar (PVDF) basilar memebrane that is even, being 0.22 μm by the aperture impregnated with deionized water 3 days by vacuum filtration method
Load mixing film liquid is to get MB/g-C3N4Composite membrane.60 DEG C of drying 12h remove excess of solvent.
5, the MB/g-C of the present embodiment3N4Application of the composite membrane in nanofiltration: by the above-mentioned MB/g-C for being carried on PVDF3N4
Composite membrane is fixed in filter device, and concentration is 10 μm of ol/L electronegative EB (azovan blue) aqueous solutions, water flux
1828L·h-1·m-2·bar-1, the rejection of azovan blue is 98.5%；Concentration is the positively charged RB (rhodamine of 10 μm of ol/L
B) aqueous solution, water flux 1312Lh-1·m-2·bar-1, the rejection of rhodamine B is 88.0%.
The limitation that technical solution of the present invention is not limited to the above specific embodiments, it is all to do according to the technique and scheme of the present invention
Technology deformation out, all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of anionic compound intercalation g-C3N4The preparation method of composite membrane, it is characterised in that:
Body phase g-C is obtained by thermal polymerization method first3N4；It removes to obtain g-C using physics3N4Nanometer sheet dispersion liquid；Finally
By anionic compound and g-C3N4Nanometer sheet dispersion liquid mixed deposit is inserted on perforated substrate film to get to anionic compound
Layer g-C3N4Composite membrane.
2. preparation method according to claim 1, it is characterised in that include the following steps:
Step 1: the melamine or urea for weighing 1-5g, which are placed in mortar, grinds 10-20min, be subsequently placed in Muffle furnace in
8-12h is calcined at 500-600 DEG C, obtains body phase g-C3N4；
Step 2: the body phase g-C that step 1 is obtained3N4Grind into powder is configured to g-C3N4Suspension, heating ultrasound, then in
20min is centrifuged under 8000rpm, centrifugation leaves and takes supernatant three times, obtains the g-C of stable dispersion3N4Nanometer sheet dispersion liquid；
Step 3: the g-C that step 2 obtains3N4Nanometer sheet dispersion liquid and the mixing of anionic compound solution, heat ultrasound 10-20min
It is uniformly mixed it, pretreated perforated substrate film is loaded to get anion by mixing film liquid by nanometer sheet package technique
Compound intercalation g-C3N4Composite membrane, drying removal excess of solvent.
3. preparation method according to claim 2, it is characterised in that:
In step 2, g-C3N4The concentration of suspension is 3-6mg/mL；The temperature of heating ultrasound is 80-120 DEG C, and ultrasonic time is
10-18h。
4. preparation method according to claim 2, it is characterised in that:
In step 3, the anionic compound solution is sulfonated polyphenyl ethereal solution, azovan blue solution or methyl blue solution；Institute
The concentration for stating anionic compound solution is 1mg/mL.
5. preparation method according to claim 2 or 4, it is characterised in that:
In step 3, g-C3N4The mass ratio of nanometer sheet dispersion liquid and anionic compound solution is 1:0.5-1:10.
6. preparation method according to claim 2, it is characterised in that:
In step 3, the perforated substrate film include poly (ether sulfone) film, polyvinylidene fluoride film, polycarbonate membrane, anodic alumina films,
One of polyacrylonitrile film etc., and the aperture of porous carrier is 100-450nm.
7. preparation method according to claim 2, it is characterised in that:
In step 3, the drying is in 40-80 DEG C of dry 8-15h.
8. preparation method according to claim 2, it is characterised in that:
The anionic compound intercalation g-C of preparation3N4Composite membrane with a thickness of 200nm-1 μm.
9. the anionic compound intercalation g-C of any method preparation in claim 1-83N4The application of composite membrane, feature exist
In: the composite membrane is fixed in nanofiltration device, for retaining size and electrically charged different nanoparticle.
10. application according to claim 9, it is characterised in that:
The nanoparticle includes methylene blue, methyl blue, rhodamine B, azovan blue, methyl orange, Congo red etc..
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