CN114931864B - Two-dimensional material composite separation membrane, preparation method and application - Google Patents

Two-dimensional material composite separation membrane, preparation method and application Download PDF

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CN114931864B
CN114931864B CN202210478882.7A CN202210478882A CN114931864B CN 114931864 B CN114931864 B CN 114931864B CN 202210478882 A CN202210478882 A CN 202210478882A CN 114931864 B CN114931864 B CN 114931864B
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CN114931864A (en
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李梅生
郑涛
赵宜江
周守勇
贾明民
李悦悦
吴飞跃
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Huaiyin Normal University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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Abstract

The invention relates to a two-dimensional material composite separation membrane, a preparation method and application thereof, and belongs to the technical field of membrane separation. The two-dimensional material composite separation membrane consists of two-dimensional materials and nano materials loaded on the two-dimensional materials, wherein the two-dimensional materials are g-C 3 N 4 Nanoplatelets, the nanomaterial is MoS 2 Nanoplatelets or nano ZnO. With g-C 3 N 4 Pure film and MoS 2 Compared with the pure film, the composite film has improved retention performance of phenol and visible light catalytic degradation performance, and has better stability. The nano ZnO can effectively fill g-C 3 N 4 The crack and cavity of the film have greatly improved performance. The rejection rate of the composite membrane exceeds 88 percent, and the photocatalytic performance is g-C 3 N 4 /MoS 2 2 times of the composite film.

Description

Two-dimensional material composite separation membrane, preparation method and application
Technical Field
The invention relates to a two-dimensional material composite separation membrane, a preparation method and application thereof, and belongs to the technical field of membrane separation.
Background
Two-dimensional graphite phase carbon nitride (g-C) 3 N 4 ) Material [1,2] Have been explored as very promising candidates for the fields of photocatalytic chemistry and separation membranes. g-C 3 N 4 The nanoplatelets are free of metals, non-toxic and easy to prepare on a large scale in the laboratory. Importantly, g-C 3 N 4 Is a material with a two-dimensional lamellar structure and takes a trithiotriazine ring as a basic structural unit, g-C 3 N 4 Has Van der Waals force between the sheets, has pi-pi conjugated structure, has special electronic and photocatalysis performance, and is superior to traditional TiO 2 The photocatalyst has a wider absorption spectrum range, and does not need ultraviolet light only under common visible light to play a role in photocatalysis. g-C 3 N 4 Unique lattice defects and layered structures in nanoplatelets [3] Is very suitable for the formation of membrane channels for the selective transport of water. Zhao et al [4] Study of Complex g-C 3 N 4 Permeability of the photocatalytic film. The results show that due to g-C 3 N 4 The removal efficiency and permeation flux of rhodamine B are improved. These high separation and high permeation properties are due to g-C 3 N 4 The function of the nano-sheet. But due to g-C 3 N 4 The specific surface area of the photo-generated electron hole is small, and the photo-generated electron hole is easy to be recombined, so that the transportation speed of photo-generated carriers is low, and the photo-catalytic activity of the photo-generated carriers is limited. Thus, g-C is increased 3 N 4 Has important significance in the photocatalytic activity of the polymer.
In recent years, researchers have found that g-C is prepared by a certain preparation method 3 N 4 The block body is stripped, and 2D g-C with better photocatalytic activity can be obtained 3 N 4 A nano-sheet. Common methods are thermal oxidation corrosion exfoliation, chemical intercalation exfoliation and liquid exfoliation. However, 2D g-C prepared by thermal oxidative corrosion exfoliation 3 N 4 The nanoplatelet interface has a number of defects. In the chemical intercalation stripping process, the chemical intercalation can destroy a single-layer two-dimensional g-C 3 N 4 The structure of the nano-sheet and the process are complex. The liquid stripping method is to prepare two-dimensional g-C 3 N 4 One of the most commonly used methods for nanoplatelets has higher photocatalytic activity and mass productivity than thermal oxidation, etching stripping and chemical intercalation stripping. However, this approach still has some problems. An organic solvent is used in the exfoliation process and long ultrasonic assistance is required. Thus, this method may produce a large amount of organic waste liquid with a large amount of energy consumption. Therefore, it is important to find a stripping method which is environment-friendly and can meet the requirements of high yield and photocatalytic activity.
Self-supporting ultra-thin films have been a hotspot in research and industrial applications for decades, as such self-supporting films have a width of a few centimeters and a thickness of a few nanometers, i.e. have both macroscopic material and single molecule properties. Ran and the like [5] By MoS in two dimensions 2 Zn-BTC/MoS is successfully prepared by inserting Zn-BTC nanowire into the film 2 Composite film, the result shows that Zn-BTC/MoS 2 Flux ratio MoS of organic solvent of composite membrane 2 The membrane is improved by 6 times, and meanwhile, the composite membrane keeps excellent sieving capability, and can completely intercept dye molecules with the size larger than 0.42 nm.
Although g-C 3 N 4 There are many problems in the application of film materials, but there are still many problems in the application of self-film formation. First g-C 3 N 4 Poor film forming property of the self and the prepared g-C 3 N 4 Once the size of the pure film is oversized, the film surface will have many more pronounced defect cracks. Meanwhile, in the self-film forming process, more cavities are formed in the film. The presence of these cavities greatly affects g-C 3 N 4 Separation performance of the membrane. Second g-C 3 N 4 The radix angelicae sinensis has certain photocatalytic performance, and how to take advantage of the characteristic is a hot spot of current research.
[1]S Li,L Zhang,X Zhong,et al.Nano-subsidence-assisted precise integration of patterned two-dimensional materials for high-performance photodetector arrays[J].ACS Nano,2019.
[2]Y Zhe,J D Benck,Y Eatmon,et al.Stable,temperature-dependent gas mixture permeation and separation through suspended nanoporous single-layer graphene membranes[J].Nano Letters,2018,18(8):5057-5069.
[3]Y Wang,L Li,Y Wei,et al.Water transport with ultralow friction through partially exfoliated g-C 3 N 4 nanosheet membranes with self-supporting spacers[J].Angewandte Chemie International Edition,2017,56(31):8974-8980.
[4]H Zhao,S Chen,X Quan,et al.Integration of microfiltration and visible-light-driven photocatalysis on g-C3N4 nanosheet/reduced graphene oxide membrane for enhanced water treatment[J].Applied Catalysis B Environmental,2016,194:134-140.
[5]Ran, huang Jiang, ai Xinyu, et al Zn-BTC/MoS 2 Composite two-dimensional membrane construction and organic solvent nanofiltration performance research [ J ]]Chemical journal 2021,04:2148-2155.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: existing g-C 3 N 4 Poor film forming property of the self and the prepared g-C 3 N 4 Once the size of the pure film is oversized, the film surface will have many more pronounced defect cracks. Meanwhile, in the self-film forming process, more cavities are formed in the film. The presence of these cavities greatly affects g-C 3 N 4 Separation performance of the membrane. By combining MoS 2 Nano ZnO and g-C 3 N 4 Nanometer sheet is compounded to prepare MoS 2 /g-C 3 N 4 Film g-C 3 N 4 The @ ZnO film is prepared, and the performance of the prepared film is researched, so that the retention of the composite film on phenol and the visible light catalytic degradability are effectively improved.
The second technical problem to be solved by the invention is as follows: solves the problem of 2D g-C prepared in the prior art 3 N 4 The method of the nano-sheet has the problems of low yield, high energy consumption and the like. It is proposed to prepare g-C by gas phase exfoliation 3 N 4 Recipe of nano-sheetA method of manufacturing the same. Exfoliated g-C 3 N 4 The nano-sheet has thinner sheet layer, and partial sheet layer thickness can reach the single sheet layer. The structure is complete and the size is large.
The technical proposal is as follows:
a first object of the present invention is to provide:
two-dimensional g-C 3 N 4 The nano-sheet is prepared by a gas phase exfoliation method.
A second object of the present invention is to provide:
the two-dimensional g-C 3 N 4 The preparation method of the nano-sheet comprises the following steps:
step 1, g-C 3 N 4 Heating the powder, and adding the product into liquid nitrogen;
step 2, dispersing the product obtained in the step 1 in ethanol water solution, uniformly stirring, and then performing first centrifugal treatment to obtain supernatant;
step 3, performing a second centrifugation treatment on the supernatant obtained in the step 2 to obtain a precipitate, and drying to obtain two-dimensional g-C 3 N 4 A nano-sheet.
The temperature rise in the step 1 is to raise the temperature to 300-500 ℃, and the step 1 is repeated for 1-20 times.
The first centrifugation in step 2 is repeated 1-10 times at 4000-5500rpm.
The centrifugation speed of the second centrifugation in step 3 is 10000-15000rpm.
Said g-C 3 N 4 The powder is prepared by a thermal polymerization method.
The steps of the thermal polymerization method comprise: calcining melamine, grinding, cleaning and drying the product to obtain g-C 3 N 4 And (3) powder.
The calcination process is that the calcination is carried out for 1-10 hours at 500-600 ℃.
The cleaning process is to sequentially clean with deionized water and absolute ethyl alcohol.
The drying is carried out at 60-100deg.C for 1-48h.
A third object of the present invention is to provide:
the two-dimensional g-C 3 N 4 Use of nanoplatelets for photocatalytic degradation of organic matter.
The organic matter is phenol.
In the photocatalytic degradation, a visible light source is adopted for irradiation.
A fourth object of the present invention is to provide:
a two-dimensional material composite separation membrane consists of two-dimensional materials and nano materials loaded on the two-dimensional materials, wherein the two-dimensional materials are g-C 3 N 4 Nanoplatelets, the nanomaterial is MoS 2 Nanoplatelets or nano ZnO.
In one embodiment, the weight ratio of the two-dimensional material to the nanomaterial is in the range of 1:9-9:1.
a fifth object of the present invention is to provide:
a preparation method of a two-dimensional material composite separation membrane comprises the following steps:
step 1, preparing two-dimensional g-C 3 N 4 Dispersion of nanoplatelets and two-dimensional MoS 2 A dispersion of nanoplatelets;
step 2, two-dimensional g-C 3 N 4 Dispersion of nanoplatelets and two-dimensional MoS 2 And mixing the dispersion liquid of the nano sheets, and carrying out suction filtration to obtain a film layer.
In one embodiment, two-dimensional g-C in step 2 3 N 4 Nanoplatelets and two-dimensional MoS 2 Weight ratio of nanosheets 1:9-9:1.
in one embodiment, in step 1, two-dimensional g-C 3 N 4 Nanoplatelets or two-dimensional MoS 2 The preparation method of the nano-sheet comprises the following steps:
step a, g-C 3 N 4 Or MoS 2 Heating the powder, and adding the product into liquid nitrogen;
step b, dispersing the product obtained in the step a in ethanol water solution, uniformly stirring, and then performing first centrifugal treatment to obtain supernatant;
step c, for the step bPerforming a second centrifugation treatment on the supernatant to obtain a precipitate, and drying to obtain two-dimensional g-C 3 N 4 Nanoplatelets or two-dimensional MoS 2 A nano-sheet.
The temperature rise in the step a is to raise the temperature to 300-500 ℃, and the step 1 is repeated for 1-20 times.
The first centrifugation in step b is repeated 1-10 times at 4000-5500rpm.
The centrifugation speed of the second centrifugation in step c is 10000-15000rpm.
A sixth object of the present invention is to provide:
a preparation method of a two-dimensional material composite separation membrane comprises the following steps:
step 1, preparing two-dimensional g-C 3 N 4 A dispersion of nanoplatelets;
step 2, zn (NO) is added to the dispersion 3 ) 2 Filtering to form a film;
step 3, soaking the film layer obtained in the step 2 in Zn (NO 3 ) 2 Soaking in NaOH solution, taking out, and calcining to obtain the composite separation membrane.
In one embodiment, zn (NO 3 ) 2 And g-C 3 N 4 The weight ratio of the nano-sheets is 5-15:1.
in one embodiment, in step 3, zn (NO 3 ) 2 The concentration of the solution is 1-50mg/ml, and the concentration of the NaOH solution is 0.1-2mol/L.
A seventh object of the present invention is to provide:
the application of the two-dimensional material composite separation membrane in filtering and/or photocatalytic decomposition of organic matter-containing solution.
An eighth object of the present invention is to provide:
ZnO and/or MoS 2 Nanoflakes for repair of g-C 3 N 4 Use of surface defects of films.
A ninth object of the present invention is to provide:
ZnO and/or MoS 2 Use of nanosheets for increasing g-C 3 N 4 Film pairUse in the rejection rate of organic matter in solution.
Advantageous effects
(1) Preparation of g-C 3 N 4 In the nano-sheet method, the material is heated by the gas phase exfoliation method. The high temperature can cause the sheets of material to vibrate in an accelerated manner, thereby increasing the spacing between the sheets. When the supercooled liquid gas enters between the sheets, it is vaporized drastically and expands rapidly. The gas molecules collide with the lamellae, creating a force that separates the lamellae. Liquid nitrogen is typically used as the vaporization medium. Because the liquid nitrogen is very low in temperature and low in cost. The vapor phase exfoliation process is simpler and more environmentally friendly.
(2) Exfoliated g-C 3 N 4 The nano-sheet has thinner sheet layer, and partial sheet layer thickness can reach the single sheet layer. The structure is complete and the size is large. Compared with the traditional exfoliation method, the gas phase exfoliation method is in g-C 3 N 4 The structural performance of the nano sheet is obviously improved.
(3) Preparation of g-C by different heating temperatures versus gas phase exfoliation 3 N 4 The effect of the nanoplatelets is different. The higher the heating temperature, the higher the effect and yield of exfoliation. When the temperature reached 500 ℃, there was a significant increase in flaking effect and yield.
(4)g-C 3 N 4 Can degrade phenol by photocatalysis at room temperature. g-C 3 N 4 The catalytic rate of the nano-sheet is non-exfoliated g-C 3 N 4 2-3 times of (3). Preparation of g-C by gas phase exfoliation 3 N 4 The nano-sheet can effectively improve g-C 3 N 4 Photocatalytic properties.
(5) With g-C 3 N 4 Pure film and MoS 2 Compared with the pure film, the composite film has improved retention performance of phenol and visible light catalytic degradation performance, and has better stability.
(6) When g-C 3 N 4 And MoS 2 g-C when the mass ratio is 1:1 3 N 4 /MoS 2 The composite film performance improves best. The retention rate is greatly improved compared with a pure membrane, and the retention rate of phenol is 42.1 percent. At the same time, the visible light catalytic performance is the same as g-C 3 N 4 Compared with pure film, g-C 3 N 4 1.5 times of the pure film, the same as MoS 2 Compared with pure film, is MoS 2 3 times of the pure film.
(7) The nano ZnO can effectively fill g-C 3 N 4 The crack and cavity of the film have greatly improved performance. The rejection rate of the composite membrane exceeds 88 percent, and the photocatalytic performance is g-C 3 N 4 /MoS 2 2 times of the composite film.
Drawings
FIG. 1 is a schematic diagram of a vapor phase exfoliation process for preparing g-C 3 N 4 Schematic of the nanoplatelet principle.
FIG. 2 is a block g-C 3 N 4 And g-C 3 N 4 Infrared spectrogram of the nanometer sheet.
FIG. 3 shows an X-ray diffraction analysis of a block of g-C 3 N 4 g-C 3 N 4 Crystal structure of nanosheets
FIG. 4 is a graph showing particle size distribution.
FIG. 5 is a block g-C 3 N 4 And g-C3N4 nanosheets (60 days)
FIG. 6 is an ultraviolet fluorescence test chart (left: block g-C) 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Right: CN-500)
FIG. 7 shows that (a) and (b) are block-shaped g-C 3 N 4 SEM images of (a); (c) In the form of blocks g-C 3 N 4 A TEM image of (a); (d) Is g-C 3 N 4 TEM image of nanoplatelets
FIG. 8 is a graph of illumination time versus block g-C 3 N 4 Influence of photocatalytic degradation of phenol by CN-500
Fig. 9: g-C 3 N 4 /MoS 2 Composite membrane preparation flow chart
Fig. 10: g-C 3 N 4 Electrostatic distribution diagram
Fig. 11: g-C 3 N 4 /MoS 2 Composite membrane preparation flow chart
Fig. 12: process flow diagram for pervaporation
Fig. 13: g-C 3 N 4 /MoS 2 SEM (scanning electron microscope) image and EDS (electron discharge machining) elemental analysis of surface and section of composite membrane
Fig. 14: g-C 3 N 4 SEM (scanning electron microscope) graph and EDS (electron beam diffraction) elemental analysis of surface and section of @ ZnO composite film
Fig. 15: different MoS 2 g-C content 3 N 4 /MoS 2 Influence of composite Membrane on phenol rejection Properties
Fig. 16: g-C 3 N 4 And MoS 2 g-C with a mass ratio of 1:1 3 N 4 /MoS 2 Cyclic test of composite membrane retention for phenol figure 17: g-C 3 N 4 Cyclic test chart of retention performance of phenol by @ ZnO composite film cyclic test chart
Fig. 18: performance graph of visible light catalytic degradation of phenol
Fig. 19: and (5) preparing a mechanism diagram of the composite film. (a): g-C 3 N 4 /MoS 2 A composite membrane; (b): g-C 3 N 4 @ZnO composite film
Detailed Description
Preparation of g-C in gas phase stripping 3 N 4 The reagents and instruments used in the nanosheet experiments are shown in tables 1 and 2, respectively:
TABLE 1 Experimental reagents
Table 2 laboratory apparatus
Method for preparing g-C by thermal polymerization 3 N 4
Experimental method for preparing a large amount of g-C by adopting thermal polymerization method 3 N 4 And (3) powder. The specific experimental steps are as follows: firstly, weighing 10g of melamine and placing the melamine in an alumina crucible with a cover; then placing the crucible in a tube furnace, and calcining for 4 hours at 550 ℃ (the heating rate is 5 ℃/min); the calcined product is light yellow massive solid, and after being ground in a mortar, the calcined product is washed with deionized water and absolute ethyl alcohol for three times to remove unreacted impurities; drying at 80deg.C for 24 hr to obtain g-C 3 N 4 And (3) powder.
Preparation of g-C by gas phase exfoliation 3 N 4 Nanosheets
Weighing 5g of prepared g-C 3 N 4 The powder is placed in a crucible. The tube furnace was then warmed to 300 ℃. The crucible was placed in a heated tube furnace and heated for 10min. Pouring 100ml of liquid nitrogen into a 500ml polytetrafluoroethylene beaker, and heating the g-C 3 N 4 The powder was rapidly added to liquid nitrogen. The beaker was shaken until the liquid nitrogen was completely vaporized. This is a complete exfoliation process. The above experimental procedure was repeated until the 10 th exfoliation was completed. 500ml of ethanol/water solution (volume ratio 1:1) was added to a beaker of polytetrafluoroethylene. After stirring with a glass rod for 5min, the mixture was dispersed by ultrasound for 30min. The dispersion was centrifuged using an electric precipitation centrifuge. The rotation speed was 4800rpm. Centrifuging the supernatant under the same conditions, and repeating for 5 times to obtain g-C 3 N 4 A nanosheet dispersion. Taking g-C 3 N 4 The nanoplatelet dispersion is subjected to high speed centrifugation. The rotation speed was 12000rpm. Vacuum drying the precipitate at 80deg.C for 12 hr to obtain g-C 3 N 4 The nanoplatelet powder was used for subsequent sample characterization. The sample was designated CN-300. The heating temperature was changed to 400℃and 500℃and the samples were designated CN-400 and CN-500, respectively. FIG. 1 is a schematic diagram of a vapor phase exfoliation process for preparing g-C 3 N 4 Schematic of the nanoplatelet principle.
Infrared analysis
By detecting the lump g-C 3 N 4 Powder and g-C 3 N 4 FT-IR spectrum of nanoplatelets. The peak positions of the samples are basically consistent, which indicates that the g-C is prepared by a gas phase exfoliation method 3 N 4 The nano-sheet does not change g-C 3 N 4 Is a chemical microstructure of (a). g-C 3 N 4 The presence of a large amount of primary and secondary amines at the edge portion, resulting in stretching vibration of N-H bonds, which occurs at 3600 to 3100cm -1 Is a broad peak region of (a). And g-C 3 N 4 Structure having a large number of 3-s-triazine rings inside 813cm -1 The peak at this point is caused by the vibration of the structure. 1650-1240cm -1 The peaks between correspond to the stretching vibration of the C-N bond and the C-NH-C bond, respectively. FIG. 2 is a block g-C 3 N 4 And g-C 3 N 4 Infrared spectrogram of the nanometer sheet.
XRD analysis
Analysis of the blocky g-C by X-ray diffraction 3 N 4 g-C 3 N 4 The crystal structure of the nanoplatelets (fig. 3). From the figure, it is evident that g-C 3 N 4 Two characteristic peaks (003) and (100) in the XRD spectrum of (C). The stacking structure of conjugated aromatic planes like graphite may show strong peaks around 28 °. While the repeat units inside the sheet show strong peaks at 13 deg. positions. As the temperature increases, the intensities of the (003) and (100) peaks decrease, indicating that g-C can be produced 3 N 4 A nano-sheet. The peak area at 500 ℃ is obviously smaller than 300 ℃ and 400 ℃, which shows that the peeling effect is better when the heating temperature is 500 ℃.
Particle size analysis
From the detection result, it can be clearly seen that g-C is peeled off 3 N 4 The particle size of the nano-sheet is smaller than that of the non-exfoliated g-C 3 N 4 . It is also evident that the particle size of CN-500 is significantly smaller than CN-300 and CN-400. Indicating that the heating temperature has a significant effect on the exfoliation effect. Meanwhile, the grain diameter of CN-500 can reach 290nm, which is far smaller than that of the traditional stripping process for preparing g-C 3 N 4 The particle size of the nanosheets (about 300 nm). FIG. 4 is a graph showing particle size distribution.
g-C 3 N 4 Nanosheets dispersibility and fluorescence Properties
As is evident from a comparison of the dispersion after 2 months of standing (FIG. 5), only CN-500 was well dispersed in the dispersion. While CN-300, CN-400 and non-exfoliated g-C 3 N 4 The powder had settled to the bottom of the reagent bottle. The results show that g-C is prepared by a gas phase exfoliation method 3 N 4 In the process of nano-sheet, only when the heating temperature is higher than a certain degree, the nano-sheet has good stripping effect. As can be seen from the above experimental results, the CN-500 has the best structural performance, so that the subsequent characterization test mainly detects CN-500. As can be seen in the fluorescence functional test, CN-500 has a distinct fluorescent effect under UV irradiation (FIG. 6).
SEM and TEM analysis
Observation of g-C by SEM 3 N 4 The powder structure was found to have a distinct lamellar stack. Non-exfoliated g-C 3 N 4 Presenting a massive stack state, severely affecting g-C 3 N 4 Performance. g-C after stripping can be seen by TEM 3 N 4 The sheets of the nano-sheets are thinner and can partially reach the single-sheet layer. Exfoliated g-C 3 N 4 The nano-sheet has complete structure and larger transverse dimension. The electron microscope test result shows that the gas phase spalling method can prepare g-C 3 N 4 The nano-sheet has greatly improved structural performance.
g-C 3 N 4 g-C 3 N 4 Nanosheet photocatalytic performance
An aqueous phenol solution was first prepared at a concentration of 10mg/ml. 0.1g of non-exfoliated g-C was weighed out 3 N 4 The powder was added to an aqueous phenol solution. Dispersing with light-shielding ultrasonic for 5min, stirring with light-shielding for 25min to obtain g-C 3 N 4 The particles reach adsorption equilibrium. The solution was then irradiated with a visible light source. The light source is white in color and has a power of 100w. Sampling every 0.5h, and removing g-C from the solution by using a high-speed centrifuge with a rotation speed of 12000rpm 3 N 4 . The phenol concentration was measured by UV-visible spectrophotometry at a test wavelength of 213nm and the solution was ethanol/water (volume ratio 1:1). The phenol standard curve was measured before the experiment was started. The whole experiment was run at room temperature (25 ℃). The CN-500 photocatalytic performance was operated in the same procedure.
As can be seen from FIG. 8, the block shape g-C 3 N 4 g-C 3 N 4 The nano-sheets have certain photocatalytic performance. g-C 3 N 4 The catalytic rate of the nano-sheet is larger than that of the bulk g-C 3 N 4 . The results show that g-C prepared by the gas phase exfoliation method 3 N 4 The nano-sheet effectively improves the photocatalysis performance. Experimental results also show that under certain illumination conditions, g-C 3 N 4 The VOC can be catalytically degraded at room temperature.
g-C 3 N 4 /MoS 2 Preparation of composite membranes
First, two-dimensional MoS is prepared 2 The nanometer sheet adopts a gas phase peeling method, and the experimental operation steps of the preparation are as follows: weighing 5g of prepared g-C 3 N 4 The powder is placed in a crucible. The tube furnace was then warmed to 500 ℃. The crucible was placed in a heated tube furnace and heated for 10min. 100ml of L-N are poured into a 500ml polytetrafluoroethylene beaker 2 . Heating the g-C 3 N 4 Powder is rapidly added into L-N 2 Is a kind of medium. Shake the beaker until L-N 2 Completely vaporizing. This is a complete exfoliation process. The above experimental procedure was repeated until the 10 th exfoliation was completed. 500ml of ethanol/water solution (volume ratio 1:1) was added to a beaker of polytetrafluoroethylene. After stirring with a glass rod for 5min, the mixture was dispersed by ultrasound for 30min. The dispersion was centrifuged using an electric precipitation centrifuge. The rotation speed was 4800rpm. Centrifuging the supernatant under the same conditions, and repeating for 5 times to obtain g-C 3 N 4 A nanosheet dispersion. Taking g-C 3 N 4 The nanoplatelet dispersion is subjected to high speed centrifugation. The rotation speed was 12000rpm. Vacuum drying the precipitate at 80deg.C for 12 hr to obtain g-C 3 N 4 Powder of nanoplatelets. The sample was designated CN-500.
In addition, there is also a need for a MoS to be purchased 2 Stripping the powder into MoS 2 The nano-sheet also adopts a gas phase exfoliation method, and comprises the following steps: weighing 5g of prepared MoS 2 The powder is placed in a crucible. The tube furnace was then warmed to 400 ℃. The crucible was placed in a heated tube furnace and heated for 15min. 100ml of L-N are poured into a 500ml polytetrafluoroethylene beaker 2 . Heating the MoS 2 Powder is rapidly added into L-N 2 Is a kind of medium. Shake the beaker until L-N 2 Completely vaporizing. This is a complete exfoliation process. Repeating the above experimental steps until the 8 th exfoliation is finished. 500ml of ethanol/water solution (volume ratio 1:1) was added to a beaker of polytetrafluoroethylene. After stirring with a glass rod for 5min, the mixture was dispersed by ultrasound for 30min. The dispersion was centrifuged using an electric precipitation centrifuge. The rotation speed was 4000rpm. Centrifuging the supernatant under the same conditions, and repeating for 5 times to obtain MoS 2 A nanosheet dispersion. Taking MoS 2 The nanoplatelet dispersion is subjected to high speed centrifugation. The rotation speed is 10000rpm. Vacuum drying the precipitate at 85deg.C for 10 hr to obtain MoS 2 Powder of nanoplatelets.
The above g-C 3 N 4 Nanoplatelets and MoS 2 The nano-sheets are dispersed in deionized water to obtain a dispersion liquid.
Next, the preparation of the composite film is performed as follows: dispersion of CN-500 and MoS 2 The nano-sheet dispersion liquid is mixed according to a certain mass ratio and dispersed for 30min by ultrasonic. And (3) carrying out vacuum filtration to form a membrane, wherein a PVDF membrane with the thickness of 0.22 mu m is adopted in the suction filtration process, and the PVDF membrane is used as a supporting layer and is used as a composite membrane after the nano-sheet is trapped. Preparation of g-C of film Material 3 N 4 Nanoplatelets (CN-500) and MoS 2 The total content of the nano-sheets is 10mg. g-C 3 N 4 Nanosheets and MoS 2 The nanoplatelet mass ratio is set to 10:0, 9:1, 8:2, 6:4, 5:5, 4:6, 2:8, 1:9, 0:10. FIG. 9 is g-C 3 N 4 /MoS 2 And (5) preparing a composite membrane.
At 10:0 and 0:10, the films prepared at a ratio of pure g-C 3 N 4 Membrane and pure MoS 2 And (3) a film.
g-C 3 N 4 Preparation of @ ZnO composite film
The method for preparing nano ZnO is many, and a proper mode is needed to be selected to prepare g-C with good performance 3 N 4 @ ZnO composite film. How the zinc source is introduced is of paramount importance. By molecular modeling, for g-C 3 N 4 The charge distribution and electrostatic potential distribution of (C) were calculated to find g-C 3 N 4 The unique lattice defect hole is surrounded by negative potential. By introducing Zn 2+ Is to adsorb Zn by electrostatic potential 2+ After the subsequent reaction, nano ZnO is formed. In addition, zn can be adsorbed by multi-channel adsorption of membrane autogenous 2+ . Fig. 10 shows an electrostatic distribution diagram, 1 being a positive potential, 2 being a negative potential, and 3 being neutral. Selecting Zn (NO) 3 ) 2 As a zinc source, because Zn (NO 3 ) 2 The highest degree of dissociation in ethanol/water solution.
Taking a certain amount of g-C 3 N 4 Nano-sheetCN-500) dispersion, the content of CN-500 was 10mg. 0.1g of Zn (NO) was weighed out 3 ) 2 Added to the dispersion of CN-500. And magnetically stirring for 30min. And then vacuum filtration is carried out to prepare a membrane, a PVDF membrane with the thickness of 0.22 mu m is adopted in the suction filtration process, and after the nano-sheet is trapped, the PVDF membrane is used as a supporting layer and is used as a composite membrane. Soaking the membrane prepared by suction filtration in Zn (NO) with concentration of 10mg/ml 3 ) 2 Soaking in 0.5mol/L NaOH solution for 4 hr, and standing for a period of time to volatilize water. The dry film was placed in a tube furnace for calcination. The calcined film is g-C 3 N 4 @ ZnO composite film.
Comparative examples 1g to C 3 N 4 Preparation of ZnO composite film
Compared with example 2, the difference is that: directly mixing ZnO powder (average particle diameter 90 nm) with g-C 3 N 4 And mixing the nano sheets, and calcining to prepare a film. Taking a certain amount of g-C 3 N 4 The content of CN-500 in the nano-sheet (CN-500) dispersion liquid is 10mg. 0.05g of ZnO was weighed out and added to the CN-500 dispersion. And magnetically stirring for 30min. And then vacuum filtration is carried out to prepare a membrane. And (3) placing the membrane dry film prepared by suction filtration in a tube furnace for calcination. The calcined film is g-C 3 N 4 A ZnO composite film.
SEM and EDS analysis of composite membranes
Observation of g-C by scanning electron microscope 3 N 4 /MoS 2 Composite film and g-C 3 N 4 Microcosmic morphology of the @ ZnO composite film. Observation of g-C by EDS elemental analysis 3 N 4 /MoS 2 Composite film and g-C 3 N 4 And the @ ZnO composite film is formed by distributing N, mo and Zn elements.
Observation of g-C by SEM 3 N 4 /MoS 2 Composite film and g-C 3 N 4 The microstructure of the surface and the section of the @ ZnO composite film was analyzed by EDS elements, and the results are shown in FIG. 13 and FIG. 14.
From FIGS. 13 and 14, g-C can be seen 3 N 4 /MoS 2 Composite film and g-C 3 N 4 The @ ZnO composite film effectively repairs the defects of the pure film and g-C 3 N 4 @ZnO composite filmThe improvement effect is better. g-C 3 N 4 /MoS 2 The surface of the composite film still has smaller defect cracks. From EDS analysis, at g-C 3 N 4 /MoS 2 g-C in the composite film 3 N 4 And MoS 2 Are dispersed uniformly. And at g-C 3 N 4 In the @ ZnO composite film, although the surface is repaired more completely, the element distribution can show that the nano ZnO is loaded and uniformly dispersed on the surface and the inside of the film, but the amount is lower than MoS 2 。
Separation performance research and visible light catalytic performance research of composite membrane
Detection of g-C 3 N 4 /MoS 2 Composite film and g-C 3 N 4 Separation performance of the @ ZnO composite membrane. Firstly, preparing phenol solution, wherein the total amount is 40g and the mass fraction is 50%. Sampling to detect benzene concentration as reference. The separation performance of the composite membrane on phenol/water was examined by a permeation steam device. The total time was 1h. Detecting the concentration of phenol in cold hydrazine after the experiment is finished, and calculating g-C 3 N 4 The retention rate of phenol by the @ ZnO composite film.
To check the stability of the composite film, g-C was used in a mass ratio of 1:1 3 N 4 /MoS 2 Composite membrane and g-C 3 N 4 The @ ZnO composite film was subjected to 5-cycle test.
By g-C 3 N 4 /MoS 2 Composite film and g-C 3 N 4 The @ ZnO composite film degrades phenol under visible light, so that the visible light catalytic performance of the composite film is detected. First, a phenol solution was prepared at room temperature at a concentration of 10mg/ml. The composite membrane is fixed on a support. The stent with the membrane is placed in a phenol/water solution. The magnetic stirring is carried out for 30min in advance in dark, and then the white visible light source is used for irradiation. Samples were taken every 0.5h and the phenol concentration was measured with a spectrophotometer for a total time of still 4.5h.
FIG. 15 shows different g-C 3 N 4 And MoS 2 Influence of the content of composite film on the retention performance of phenol. It is clear from the graph that the retention rate of the composite membrane to phenol is highest when the mass ratio is 1:1.At the same time find that when g-C 3 N 4 Pure film and MoS 2 The flux of the pure membrane is extremely large, the retention rate is extremely low, which indicates that g-C 3 N 4 Pure film and MoS 2 Pure membranes do not meet retention performance. FIG. 16 is g-C 3 N 4 And MoS 2 g-C at a mass ratio of 1:1 3 N 4 /MoS 2 And (3) a composite membrane circulation test chart. The interception and flux change of the membrane are smaller, and the stability of the membrane is better. g-C 3 N 4 Flux of the @ ZnO composite membrane is 22356.42 g.m -2 ·h -1 The retention rate is 88.25%; by directly passing ZnO nanoparticles and g-C in comparative example 1 3 N 4 The retention rate of the composite membrane obtained by mixing the nano sheets on phenol is only 9.2 percent, and the composite membrane is prepared by mixing pure g-C 3 N 4 There was no substantial difference in the rejection of the nanoplatelets films, indicating that ZnO was directly compared to g-C through nanoparticles 3 N 4 The mixed film preparation of the nano-sheets can not improve the interception performance of the nano-sheets to phenol. The results show g-C 3 N 4 The performance of the @ ZnO composite film is higher than that of g-C 3 N 4 /MoS 2 The composite film is more prominent. FIG. 17 is g-C 3 N 4 And (3) a loop test chart of the @ ZnO composite film.
The above experimental results can be seen that g-C was modified 3 N 4 /MoS 2 g-C 3 N 4 The separation performance of the @ ZnO composite membrane is greatly improved. From the results of photocatalytic degradation of phenol, it can be seen that the modified g-C 3 N 4 /MoS 2 g-C 3 N 4 The visible light catalytic performance of the @ ZnO composite film is greatly improved, g-C 3 N 4 The visible light catalytic performance of the @ ZnO composite film is optimal. FIG. 18 is a graph showing the performance of visible light catalytic degradation of phenol.
From the experimental results, it can be found that g-C 3 N 4 Pure film and MoS 2 The performance of pure films is poor due to the characteristic of vacuum filtration of 2D nano-sheet materials to form a large number of cavities in the film, which results in the degradation of the film performance. But when g-C 3 N 4 And MoS 2 When the content is similar, the retention rate of the composite membrane is low, and the composite membrane is still improved.This may be due to g-C 3 N 4 Nanoplatelets and MoS 2 The nano sheets have different sizes and different surface charges, so that in the film forming process, the composite film has fewer cavities, and the performance of the film is improved. As can be seen from the elemental analysis of EDS, the reason is that when a zinc source is introduced, zn 2+ The film is mainly adsorbed on the surface and the cavity inside the film, so that defect cracks are effectively reduced, and the performance of the film is greatly improved. The mechanism is illustrated in fig. 19.

Claims (4)

1. A process for preparing the composite separating film of two-dimensional material from g-C 3 N 4 Nanoplatelets and supports on g-C 3 N 4 The nano ZnO on the nano sheet is characterized by comprising the following steps:
step 1, preparing two-dimensional g-C 3 N 4 A dispersion of nanoplatelets;
step 2, zn (NO) is added to the dispersion 3 ) 2 Filtering to form a film; zn (NO) 3 ) 2 And g-C 3 N 4 The weight ratio of the nano-sheets is 5-15:1, a step of;
step 3, soaking the film layer obtained in the step 2 in Zn (NO 3 ) 2 Soaking in NaOH solution, taking out, and calcining to obtain a composite separation membrane;
in the step 1, two-dimensional g-C 3 N 4 The preparation method of the nano-sheet comprises the following steps:
step a, g-C 3 N 4 Heating the powder, and adding the product into liquid nitrogen; the temperature rise in the step a is to rise to 500 ℃, and the step a is repeated for 1 to 20 times;
step b, dispersing the product obtained in the step a in ethanol water solution, uniformly stirring, and then performing first centrifugal treatment to obtain supernatant;
c, performing second centrifugation on the supernatant obtained in the step b to obtain a precipitate, and drying to obtain two-dimensional g-C 3 N 4 A nano-sheet.
2. The method for preparing a two-dimensional material composite separation membrane according to claim 1, wherein the first centrifugation treatment in step b is repeated 1 to 10 times at 4000 to 5500rpm;
the centrifugation speed of the second centrifugation in step c is 10000-15000rpm.
3. The method for producing a two-dimensional material composite separation membrane according to claim 1, wherein in step 3, zn (NO 3 ) 2 The concentration of the solution is 1-50mg/ml, and the concentration of the NaOH solution is 0.1-2mol/L.
4. The use of a separation membrane obtained by the method for preparing a two-dimensional material composite separation membrane according to claim 1 for filtering and/or photocatalytic decomposition of a solution containing organic substances.
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