CN110898679B - Filter membrane preparation method and filter membrane - Google Patents

Filter membrane preparation method and filter membrane Download PDF

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CN110898679B
CN110898679B CN201911207086.4A CN201911207086A CN110898679B CN 110898679 B CN110898679 B CN 110898679B CN 201911207086 A CN201911207086 A CN 201911207086A CN 110898679 B CN110898679 B CN 110898679B
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钟丹
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Zhuhai Dahengqin Technology Development Co Ltd
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Abstract

The embodiment of the invention provides a preparation method of a filter membrane, which comprises the following steps: preparation of SnO with three-dimensional network structure2A nanofiltration membrane; the SnO2Soaking the nano filter membrane into ethanol solution containing 0.35 millimole per liter of ZD12 molecule for sensitization for 6 hours to obtain ZD12-SnO2A nanofiltration membrane; the ZD12 molecule is bonded to the SnO via a cyanoacetoxy bond2The surface of the nano filter membrane; the structure of the ZD12 molecule is shown below:
Figure DDA0002297151550000011
the filter membrane prepared by the embodiment of the invention has the advantages of simple preparation method, high photocatalytic efficiency, good stability and convenience in recycling, and can effectively absorb light.

Description

Filter membrane preparation method and filter membrane
Technical Field
The invention relates to the field of chemical materials and the field of pollutant treatment, in particular to a filter membrane preparation method and a filter membrane.
Background
Volatile Organic Compounds (VOCs) refer to Organic Compounds with saturated vapor pressure of more than 70Pa at normal temperature and boiling point of 260 ℃ below under normal pressure, or all Organic Compounds with vapor pressure of more than or equal to 10Pa and volatility at 20 ℃, most VOCs have unpleasant special odor, toxicity, irritation, teratogenicity and carcinogenic effect, and especially benzene, toluene, formaldehyde and the like cause great harm to human health. Formaldehyde, for example, is a representative of VOCs and remains widely in chemical products such as paints and coatings. Currently, formaldehyde is reported to be leached from decorative building materials, furniture and plastic products, and becomes a ubiquitous air pollutant.
Tin dioxide (SnO)2) VOCs can be effectively removed by the photocatalysis reaction due to SnO2Has high electron mobility (240 cm)2V · s), photocatalytic activity, chemical stability, and no toxicity and low cost, and thus is commonly used as an air purification material. However, SnO2The band gap is wide (3.59eV), only ultraviolet light can be absorbed, and the ultraviolet photon flux only accounts for 3% of the entire solar spectrum. The use of artificial ultraviolet light in the photocatalysis process consumes a large amount of energy additionally, and has high economic costAnd (4) raising the yield of the tea. In addition, SnO is implanted2Electrons in the Conduction Band (CB) easily recombine with holes in the Valence Band (VB) to reduce the photocatalytic efficiency.
It can be seen that there are four typical disadvantages to conventional photocatalytic systems: 1) photo-induced charge is rapidly recombined; 2) the band gap of the metal oxide is too wide to effectively absorb photons in the visible light region; 3) materials are difficult to recycle; in addition, 4) the agglomeration of the nanoparticles is severe, reducing the surface area and inhibiting the catalytic activity of the photocatalyst, limiting its practical application.
Therefore, it is necessary to develop a photocatalytic material which has a simple preparation method, a higher degradation rate of micropollutants, better stability, and convenient recycling.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention discloses a method for preparing a filter membrane, which may include:
preparation of SnO with three-dimensional network structure2A nanofiltration membrane;
the SnO2Soaking the nano filter membrane into ethanol solution containing 0.35 millimole per liter of ZD12 molecule for sensitization for 6 hours to obtain ZD12-SnO2A nanofiltration membrane; the ZD12 molecule is bonded to the SnO via a cyanoacetoxy bond2The surface of the nano filter membrane;
the structure of the ZD12 molecule is shown below:
Figure GDA0002563831330000021
alternatively, the preparation of SnO with three-dimensional network structure2A nanofiltration membrane comprising:
depositing on the wire mesh filter element to form polycrystal SnO by a spray pyrolysis method at the temperature of 280-300 DEG C2A tin dioxide electron transport layer;
is circularly performed on the polycrystalline SnO2SnO loaded on electron transport layer2Carrying out operations of nano-particles and drying three times to obtain a first sample;
sintering the first sample at 380 ℃ for 30 minutes, and naturally cooling to 70 ℃ to obtain a second sample;
immersing the second sample in SnCl at 68 ℃2Keeping the solution in the water solution for 60 minutes to obtain a third sample;
sintering the third sample at 380 ℃ for 30 minutes, naturally cooling to 80 ℃ to obtain the SnO with the three-dimensional network structure2And (4) a nanofiltration membrane.
Alternatively, the SnO2The mass fraction of the nano particles is 36-38%.
Optionally, the cycling is performed on the polycrystalline SnO2SnO loaded on electron transport layer2The nanoparticle and drying operation was performed three times, and the step of obtaining a first sample included:
the SnO2Loading nanoparticles into the polycrystalline SnO by a stencil printing process2An electron transport layer;
loading the SnO at 150 DEG2Polycrystalline SnO of nanoparticles2Drying the electron transport layer for 15 minutes;
repeating the steps three times to obtain the first sample.
Optionally, the dense polycrystalline SnO is formed by deposition on the wire mesh filter element through spray pyrolysis at the temperature of 280-300 DEG C2A tin dioxide electron transport layer comprising:
spraying precursor solution at the temperature of 280-300 ℃ and at the position 6 cm away from the silk screen filter element to deposit and form compact polycrystalline SnO on the silk screen filter element2An electron transport layer.
Optionally, the single spray time of the spray is 60 seconds;
optionally, the number of spray cycles of the spray is 30;
optionally, the spray cycles of the sprays are spaced 30 seconds apart.
Optionally, the spray precursor solution is a solution containing 0.25 mol/l SnCl2Ethanol solution of tin chloride.
Optionally, the polycrystalline SnO2The thickness of the stannic oxide electron transport layer is80-120 nm.
The embodiment of the invention also provides ZD12-SnO2The nanofiltration membrane is prepared by the preparation method of the nanofiltration membrane ZD12-SnO 2.
The embodiment of the invention also provides SnO2Nanofiltration membrane, said SnO2The nano filter membrane is prepared by the filter membrane preparation method.
In the embodiment of the invention, the polycrystalline SnO is prepared on the wire mesh filter element2Loading SnO on the tin dioxide electron transport layer2Preparation of SnO from nanoparticles2Nanofiltration of membranes, thereby forming SnO on the membrane structure2The nano particles are fixed into a three-dimensional network structure, so that the agglomeration of the nano particles is effectively reduced, a larger specific surface area is provided, and the problems of serious agglomeration of the nano particles, surface area reduction and photocatalyst catalytic activity inhibition are avoided.
In the examples of the present invention, in SnO2Bonding ZD12 molecule with cyanoacetic acid group chemical bond to obtain ZD12-SnO through sensitization on the nano filter membrane2The nano filter membrane widens ZD12-SnO due to the allelochemical effect of ZD122The nanometer filter film absorbs visible light to ensure that ZD12-SnO2The light absorption energy of the nanofiltration membrane covers a large part of the available spectral region. ZD12-SnO prepared2The nano filter membrane has more effective separation efficiency of photo-generated charge carriers, thereby obviously enhancing the degradation efficiency of a visible light driven photocatalysis system on volatile organic compounds and avoiding the rapid recombination of photo-generated charges. Meanwhile, ZD12-SnO in cyclic utilization experiment2The nano filter membrane has high stability and is convenient to recycle.
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FIG. 1 is a flow chart of the steps of a method of preparing a filter membrane according to an embodiment of the present invention;
FIG. 2 is a flow chart illustrating the steps of another method for preparing a filter membrane according to an embodiment of the present invention;
FIG. 3 is SnO prepared in example 12SEM (scanning electron microscope) images of nanofiltration membranes;
FIG. 4 is an SEM image of a cross-section of a ZD12-SnO2 nanofiltration membrane prepared in example 1;
FIG. 5 shows ZD12-SnO prepared in example 12High resolution (Transmission electron microscope) TEM images of nanofiltration membranes;
FIG. 6 shows ZD12-SnO prepared in example 12Nanofiltration Membrane, SnO2A graph comparing the degradation rates of nanoparticles and formaldehyde degraded by visible light catalysis only;
FIG. 7 shows ZD12-SnO prepared in example 12A graph comparing the degradation rate change of the photocatalytic formaldehyde filtered by the nanofiltration membrane for multiple times;
FIG. 8 shows ZD12-SnO prepared in example 12The reaction mechanism of the nanometer filter membrane for formaldehyde photodegradation.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Referring to fig. 1, a flow chart illustrating the steps of a method for preparing a filter membrane according to the present invention is shown, and as shown in fig. 1, the method may include:
step 101: preparation of SnO with three-dimensional network structure2And (4) a nanofiltration membrane.
In the embodiment of the invention, the material is based on SnO2High electron mobility, photocatalytic activity, chemical stability, nontoxicity and low cost, and SnO is selected2Nanofiltration membranes are used as the basis for membrane preparation. Optionally, to promote SnO2The specific surface area of the nano filter membrane can prepare SnO with a three-dimensional network structure2And (4) a nanofiltration membrane. One skilled in the art may also select other nanofiltration membranes having a high specific surface area structure, a high electron mobility, a good photocatalytic activity, and the like according to specific preparation process conditions or actual application requirements, which is not specifically limited in this embodiment of the present invention.
Step 102: the SnO2Soaking the nano filter membrane into ethanol solution containing 0.35 millimole per liter of ZD12 molecule for sensitization for 6 hours to obtain ZD12-SnO2A nanofiltration membrane; the ZD12 molecule was acylated by cyanoacetic acidChemical bonding to said SnO2The surface of the nano filter membrane;
the structure of the ZD12 molecule is shown below:
Figure GDA0002563831330000051
in the examples of the present invention, the prepared SnO2The nanofiltration membrane can be sensitized by a photosensitizer, and optionally SnO2The nanofiltration membrane was immersed in a solution of ZD12 molecule in ethanol at a concentration of 0.35 mmole/L of ZD12 molecule. After 6 hours of soaking, due to SnO2The nano filter membrane has a three-dimensional net structure with high specific surface area, and a large amount of ZD12 molecules are bonded on SnO through cyanoacetic acid-based chemical bonds2On the surface of the nano-filtration membrane, in SnO2A uniform visible light absorbing layer was formed on the surface of the nanofiltration membrane, resulting in the membrane prepared in this application. Alternatively, the time of the sensitization reaction can be set by the specific process requirements of the skilled person, and the SnO can be controlled by controlling the time of the sensitization reaction2The surface of the nano filter membrane is bonded with ZD12 molecular weight.
The molecule ZD12 shown in the examples of the present invention may be obtained commercially or may be obtained by Feldt, s.m.; gibson, e.a.; gabrielsson, e.; sun, l.; boschlo, g.; hagfeldt, A.design of organic dyes and Cobalt Polypyridine Redox media for High-Efficiency Dye-Sensitized Solar cells J.Am.chem.Soc.2010,132, 16714-16724, DOI:10.1021/ja 1088869.
Referring to FIG. 2, there is shown a schematic diagram of another filter membrane preparation method according to an embodiment of the present invention, as shown in FIG. 2, step 101 includes:
step 1011: depositing on the wire mesh filter element to form polycrystal SnO by a spray pyrolysis method at the temperature of 280-300 DEG C2A tin dioxide electron transport layer.
In the embodiment of the invention, the spray pyrolysis method needs simple instruments, and reactants can better control the shape and structure of the film in the pyrolysis, so that the deposited polycrystalline SnO can be ensured2The stannic oxide electron transport layer has an ideal crystal form, and can be controlled at the reaction temperature of 280-300 ℃ to prepare corresponding polycrystalline SnO by spray pyrolysis deposition2A tin dioxide electron transport layer. Optionally, in order to make the prepared membrane have a three-dimensional mesh structure, the membrane is deposited on a wire mesh filter element, wherein, in order to adapt to the temperature condition of the environment, a 304 model stainless wire mesh filter element can be adopted, and the mesh density of the wire mesh filter element can be selected according to the specific requirements of the membrane structure.
In addition, in the embodiment of the invention, spray pyrolysis can be carried out on a microscope hot table to prepare polycrystalline SnO2The tin dioxide electron transport layer can monitor the reaction degree or effect while controlling the reaction temperature, adjust or stop the reaction in time, and improve the deposition of polycrystalline SnO2Efficiency of tin dioxide electron transport layer.
Optionally, the step 1011 includes:
spraying precursor solution at the temperature of 280-300 ℃ and at the position 6 cm away from the silk screen filter element to deposit and form compact polycrystalline SnO on the silk screen filter element2An electron transport layer.
In embodiments of the invention where spray pyrolysis is employed, the distance of the spray may optionally be from the deposited polycrystalline SnO2In the embodiment of the invention, spraying is carried out at a position 6 cm away from a silk screen filter core, so that polycrystalline SnO is guaranteed to be uniformly deposited2And the tin dioxide electron transport layer can avoid the waste of the spraying precursor solution and reduce the process cost.
Optionally, the single spray time of the spray is 60 seconds.
Optionally, the number of spray cycles of the spray is 30.
Optionally, the spray cycles of the sprays are spaced 30 seconds apart.
The inventionIn the examples, to ensure polycrystalline SnO2The tin dioxide electron transport layer is uniformly deposited, and the precursor solution can be sprayed on the screen filter element by adopting a multi-time circulating spraying mode, wherein each time of single spraying can be the same or different, for example, each time of single spraying is 60 seconds; the spraying cycle number can be determined according to the requirement of the film thickness, and the thicker the requirement of the film thickness is, the more the spraying cycle number is; in order to avoid the influence of the latter spraying on the deposition effect of the former spraying between two sprays, the spraying cycles of the single spraying can be separated by 30 seconds so as to ensure that the former spraying is fully deposited.
Optionally, the spray precursor solution is a solution containing 0.25 mol/l SnCl2Ethanol solution of tin chloride.
In practical operation, the spray precursor solution used in the spray pyrolysis method may be a solution prepared by water, ethanol or other solvents, and in the embodiment of the present invention, SnCl is used2With the ethanol solution of (a) as a precursor solution, and SnCl2Is 0.25 moles per liter, thereby controlling the deposition rate.
Optionally, the polycrystalline SnO2The thickness of the tin dioxide electron transport layer is 80-120 nanometers.
In the embodiment of the invention, polycrystalline SnO can be controlled2The thickness of the tin dioxide electron transport layer is 80-120 nanometers, wherein the thickness can be any value of 80-120 nanometers such as 80 nanometers, 90 nanometers, 100 nanometers, 110 nanometers, 120 nanometers and the like.
Step 1012: is circularly performed on the polycrystalline SnO2SnO loaded on electron transport layer2The nanoparticle and drying operation was performed three times to obtain a first sample.
In embodiments of the invention, polycrystalline SnO is deposited from a spray precursor solution2On the electron transport layer, corresponding SnO can be loaded2Nanoparticles, in order to control the SnO finally formed2The thickness of the nano filter membrane can be correspondingly controlled to SnO2Concentration of nanoparticles, e.g. SnO in the form of a viscous paste2Nanoparticle loading into polycrystalline SnO2On the electron transport layer, on the guarantee filterThe film thickness is convenient to operate, and SnO is avoided2Loss of nanoparticles.
Alternatively, the SnO2The mass fraction of the nano particles is 36-38%.
In the examples of the present invention, SnO may be limited2The mass fraction of the nano-particles is 36-38%, wherein the mass fraction can be SnO with the average particle size of 50 nm2Dispersing the nanoparticles in terpineol, and keeping the mass fraction at 36-38% to enable SnO2The nanoparticles appear as a viscous paste for subsequent loading operations.
Optionally, the step 1012 comprises:
the SnO2Loading nanoparticles into the polycrystalline SnO by a stencil printing process2An electron transport layer;
loading the SnO at 150 DEG2Polycrystalline SnO of nanoparticles2Drying the electron transport layer for 15 minutes;
repeating the steps three times to obtain the first sample.
In the embodiment of the invention, SnO can be prepared by a stencil printing method2Nanoparticle loading into polycrystalline SnO2The electronic transmission layer is prepared by printing SnO with silk screen as plate material2The nano particles are uniformly deposited on the conductive substrate polycrystalline SnO through the meshes of the silk screen under the action of the scraper2Drying the electron transport layer. Optionally, to ensure SnO2The nanoparticles are stably, sufficiently and uniformly deposited, and can be reloaded and dried after drying, and the loading and drying are repeated for a plurality of times, such as three times, to obtain a first sample.
Step 1013: and sintering the first sample at 380 ℃ for 30 minutes, and naturally cooling to 70 ℃ to obtain a second sample.
Step 1014: immersing the second sample in SnCl at 68 ℃2The mixture was kept in the aqueous solution for 60 minutes to obtain a third sample.
Step 1015: sintering the third sample at 380 ℃ for 30 minutes, and naturally cooling to 80 ℃ to obtain the third sampleNetwork-like structure of said SnO2And (4) a nanofiltration membrane.
In the embodiment of the present invention, parameters in the preparation method, such as temperature, concentration, time, frequency, and the like, are all optimal conditions in an actual preparation process, and a person skilled in the art can appropriately adjust various parameter values in a reasonable range according to actual process conditions and required factors in a specific preparation process, which is not specifically limited in the embodiment of the present invention.
The embodiment of the invention also provides ZD12-SnO2Nanofiltration membrane of ZD12-SnO2The nanofiltration membrane is prepared by the preparation method of the filtration membrane shown in the figure 1.
The embodiment of the invention also provides SnO2Nanofiltration membrane, the SnO2The nanofiltration membrane is prepared by the preparation method of the filtration membrane shown in the figure 2.
In the embodiment of the invention, the polycrystalline SnO is prepared by deposition on the wire mesh filter element2Loading SnO on the tin dioxide electron transport layer2Preparation of SnO from nanoparticles2Nanofiltration of membranes, thereby forming SnO on the membrane structure2The nano particles are fixed into a three-dimensional network structure, so that the agglomeration of the nano particles is effectively reduced, a larger specific surface area is provided, and the problems of serious agglomeration of the nano particles, surface area reduction and photocatalyst catalytic activity inhibition are avoided.
In the embodiment of the invention, SnO with three-dimensional network structure2Bonding ZD12 molecule with cyanoacetic acid group chemical bond to obtain ZD12-SnO through sensitization on the nano filter membrane2The nano filter membrane widens ZD12-SnO due to the allelochemical effect of ZD122The nanometer filter film absorbs visible light to ensure that ZD12-SnO2The light absorption energy of the nanofiltration membrane covers a large part of the available spectral region. ZD12-SnO prepared2The nano filter membrane has more effective separation efficiency of photo-generated charge carriers, thereby obviously enhancing the degradation efficiency of a visible light driven photocatalysis system on volatile organic compounds and avoiding the rapid recombination of photo-generated charges. Meanwhile, ZD12-SnO in cyclic utilization experiment2The nano filter membrane has high stability and is convenient to recycle.
Preferred embodiments of the present invention will be described in detail below with reference to specific examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Depositing on a precleaned stainless steel wire mesh filter element by a spray pyrolysis method on a hot bench at 300 ℃ to form compact polycrystalline SnO2An electron transport layer. The spraying precursor solution contains 0.25M SnCl2The ethanol solution of (1). Spraying distance of 6 cm from a sample, single spraying time of 60 seconds, spraying cycle times of 30 times, and interval of 30 seconds between each cycle, and controlling the parameters to obtain the dense polycrystalline SnO with the thickness of about 100 nanometers2An electron transport layer;
mixing viscous paste-like SnO2Nanoparticles (average particle size 50 nm, diluted 36% by mass with terpineol to a viscous paste) were loaded into dense polycrystalline SnO by a stencil printing method2This operation was repeated 3 times on the electron transport layer, and after each cycle, the layer was dried in an oven at 150 ℃ for 15 minutes, and then the sample was sintered at 380 ℃ for 30 minutes in a muffle furnace, followed by natural cooling to 70 ℃, and then the sample was immersed in a 20mM aqueous solution of SnCl2 and placed in an oven at 68 ℃ for 60 minutes to ensure the state of SnO2Formation of fine SnO between nanoparticles2Fully connecting all particles by using crystals, then washing the surface of a sample by using deionized water, repeating the sintering process again, naturally cooling to 80 ℃, and finally obtaining mesoporous SnO with the thickness of about 10 micrometers2A nanofiltration membrane;
the obtained mesoporous SnO2The nanometer filter membrane is immersed into 0.35mM ethanol solution of ZD12 photosensitizer for sensitizationTake for 6 hours to enable SnO2Obtaining high ZD12 coverage rate on the surface of the filter membrane, washing the sample with absolute ethyl alcohol and drying the sample with compressed air to prepare ZD12-SnO2And (4) a nanofiltration membrane.
Reference to FIG. 3 is SnO prepared in example 12SEM image of nanofiltration Membrane, it can be seen that SnO2The nano filter membrane has an obvious mesoporous structure and a high specific surface area, so that nano particles are not easy to agglomerate.
With reference to FIG. 4, ZD12-SnO prepared in example 12SEM image of the cross section of the nano filter membrane can show that ZD12-SnO2The thickness of the nanometer filter membrane is about 10 microns, and the nanometer particles are deposited uniformly.
With reference to FIG. 5, ZD12-SnO prepared in example 12High resolution TEM image of the nanofiltration Membrane, as shown in FIG. 5, it can be seen that ZD12-SnO was sensitized2Microscopic nanostructure of nanofiltration membranes.
Example 2
The examples of the present invention also provide ZD12-SnO prepared in the above example 12The nano filter membrane is used for researching the catalytic degradation performance of volatile organic matter light, such as benzene, toluene, formaldehyde and the like, in a photocatalytic system, wherein the formaldehyde is taken as an example:
adding 100L of air containing formaldehyde into quartz reactor, circulating and passing through filter membrane repeatedly, wherein the initial formaldehyde concentration is 0.1-12mg/L, the initial humidity is 10-260%, and the formaldehyde air flow rate is 10-260m3H is used as the reference value. The adsorption experiment was first carried out in the dark for 15 minutes to achieve sufficient contact between the formaldehyde and the photocatalyst to establish an adsorption equilibrium.
Alternatively, 100L of formaldehyde-containing air may be introduced into the quartz reactor and circulated back and forth through the filter membrane, with an initial formaldehyde concentration of 10mg/L, an initial humidity of 72%, and an aldehyde-containing air flow rate of 200m3H is used as the reference value. The adsorption experiment was first carried out in the dark for 15 minutes to achieve sufficient contact between the formaldehyde and the photocatalyst to establish an adsorption equilibrium.
Will be provided with filters (>420nm) is horizontally placed outside a quartz reactor to be used as a visible light source, and the visible light source is measured by a photon densitometer to be ZD12-SnO2The average light intensity of the surface of the nano filter membrane is 100mW/cm2I.e. a standard solar intensity (am1.5g). In order to maintain a constant quartz reaction temperature, a cooling water circulation system is applied around the quartz reactor. And ordinary SnO is carried out by adopting an air pump2Nanoparticles, control experiment with air circulation flow with no SnO2 nanoparticles decomposed only photocatalytically.
Finally, the formaldehyde concentration changes were monitored and analyzed by gas chromatography.
The experimental results show that: visible light at a standard solar intensity (>400nm), the initial concentration of formaldehyde is 10mg/L, the initial humidity is 72 percent, and the air flow rate containing aldehyde is 200m3Under the condition of/h, ZD12-SnO2The efficiency of the nanofiltration membrane in degrading formaldehyde after 105 minutes was 98%.
FIG. 6 shows ZD12-SnO prepared in example 12Nanofiltration Membrane, SnO2The comparison graph of the degradation rate of the nano particles and the degradation rate of formaldehyde through visible light catalysis only shows that formaldehyde molecules are relatively stable in the air, the concentration of the formaldehyde molecules is not greatly changed after the formaldehyde molecules are irradiated for 105 minutes under the illumination condition, and the formaldehyde is ordinary SnO2The nano particles can only be degraded and removed by about 14 percent, however, ZD12-SnO2The concentration of the nanofiltration membrane on formaldehyde is greatly reduced, and the degradation efficiency can reach 98%.
FIG. 7 shows ZD12-SnO prepared in example 12And (5) comparing the degradation rate change of the photocatalytic formaldehyde filtered by the nano filter membrane for multiple times. It can be seen that ZD12-SnO prepared in example 1 was degraded in five consecutive degradation experiments2The photocatalytic degradation efficiency of the nanofiltration membrane to formaldehyde is almost kept consistent, namely ZD12-SnO2The photocatalytic activity of the filter membrane still keeps good after five cycles, and ZD12-SnO prepared by the embodiment of the invention2The filter membrane has good stability and can be recycled.
In the examples of the present invention, ZD12-SnO prepared in example 1 was shown in FIG. 82The reaction mechanism diagram of the nanometer filter membrane for formaldehyde photodegradation. As shown in FIG. 8, ZD12-SnO was exposed to light2ZD12 visible light absorption layer bonded on the surface of the nano filter absorbs visible light, electrons are excited from the Highest Occupied Molecular Orbital (HOMO) of ZD12 to the Lowest Unoccupied Molecular Orbital (LUMO), and then injected into SnO2Of a guide beltThe formation of free electrons (e-CB) in (CB) enhances the steric physical separation of the photoinduced electrons from the holes (h + ZD12) in the oxidation state ZD12, so that direct oxidation of part of the formaldehyde by h + ZD12 can also occur. At the same time, most of the e-CB is coated with SnO, except for a few complexes between e-CB and h + ZD122Oxygen (O) of the surface2) Capture and form a superoxide radical (O) with nonselective strong oxidizing property2 -) Further, the formaldehyde is oxidatively degraded. Further, a part of O2 -Subsequent conversion to H by reaction with water in the air2O2And further forms hydroxyl free radicals (OH), and the oxidation potential of OH is higher, so that the OH is more oxidative and more powerful, and the formaldehyde is efficiently oxidized and degraded. The free radicals attack volatile organics and produce several intermediates. Finally, the small molecule intermediate is completely mineralized into CO2And H2And O. In addition, when h + ZD12 directly oxidizes formaldehyde or intermediates, electrons reduce the oxidation state ZD12 to regenerate it so that the photocatalyst can reenter the next photocatalytic cycle.
In the examples of the present invention, in SnO2Bonding ZD12 molecule with cyanoacetic acid group chemical bond to obtain ZD12-SnO through sensitization on the nano filter membrane2The nano filter membrane widens ZD12-SnO due to the allelochemical effect of ZD122The nanometer filter film absorbs visible light to ensure that ZD12-SnO2The light absorption energy of the nanofiltration membrane covers a large part of the available spectral region. ZD12-SnO prepared2The nano filter membrane has more effective separation efficiency of photo-generated charge carriers, thereby obviously enhancing the degradation efficiency of a visible light driven photocatalysis system on volatile organic compounds and avoiding the rapid recombination of photo-generated charges. Meanwhile, ZD12-SnO in cyclic utilization experiment2The nano filter membrane has high stability and is convenient to recycle.
For simplicity of description, the method embodiments are described as a series of operational combinations, but those skilled in the art will recognize that the invention is not limited by the order of operation, as some steps may occur in other orders or concurrently in accordance with the invention. Further, those skilled in the art will also appreciate that the embodiments described in the specification are presently preferred and that no requirement is necessarily placed on the invention for the exact operation and experimental conditions involved.
The filter membrane and the preparation method thereof provided by the invention are described in detail above, and the principle and the implementation mode of the invention are explained in the text by applying specific examples, and the description of the above examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims (9)

1. A method for preparing a filter membrane, which is characterized by comprising the following steps:
depositing on the wire mesh filter element to form polycrystal SnO by a spray pyrolysis method at the temperature of 280-300 DEG C2An electron transport layer;
is circularly performed on the polycrystalline SnO2SnO loaded on electron transport layer2Carrying out operations of nano-particles and drying three times to obtain a first sample;
sintering the first sample at 380 ℃ for 30 minutes, and naturally cooling to 70 ℃ to obtain a second sample;
immersing the second sample in SnCl at 68 ℃2Keeping the solution in the water solution for 60 minutes to obtain a third sample;
sintering the third sample at 380 ℃ for 30 minutes, and naturally cooling to 80 ℃ to obtain SnO with a three-dimensional network structure2A nanofiltration membrane;
the SnO2Soaking the nano filter membrane into ethanol solution containing 0.35 millimole per liter of ZD12 molecule for sensitization for 6 hours to obtain ZD12-SnO2A nanofiltration membrane; the ZD12 molecule is bonded to the SnO via a cyanoacetoxy bond2The surface of the nano filter membrane;
the structure of the ZD12 molecule is shown below:
Figure FDA0002579823260000011
2. the method of claim 1, wherein said SnO2The nanoparticles are dispersed in terpineol with a mass fraction of 36-38%.
3. The method of claim 1, wherein the cycling is performed on the polycrystalline SnO2SnO loaded on electron transport layer2The nanoparticle and drying operation was performed three times, and the step of obtaining a first sample included:
the SnO2Loading nanoparticles into the polycrystalline SnO by a stencil printing process2An electron transport layer;
loading the SnO at 150 DEG2Polycrystalline SnO of nanoparticles2Drying the electron transport layer for 15 minutes;
repeating the steps three times to obtain the first sample.
4. The method as claimed in claim 1, wherein the polycrystalline SnO deposited on the wire mesh filter core by spray pyrolysis at a temperature of 280-300 ℃ is formed2A step of an electron transport layer comprising:
spraying precursor solution at the position 6 cm away from the screen filter core at the temperature of 280-300 ℃ to deposit and form polycrystalline SnO on the screen filter core2An electron transport layer.
5. The method of claim 4,
the single spray time of the spray is 60 seconds;
the spraying cycle number of the spraying is 30 times;
the spray cycle interval of the spray was 30 seconds.
6. The method of claim 4, wherein the spray precursor solution is at least one solution containing 0.25 moles of SnCl per liter2Ethanol solution of stannic chlorideAnd (4) liquid.
7. The method of claim 1, wherein the polycrystalline SnO is2The thickness of the electron transport layer is 80-120 nm.
8. ZD12-SnO2Nanofiltration membrane, characterized in that ZD12-SnO2Nanofiltration membrane prepared by a process for the preparation of a filtration membrane according to any of the preceding claims 1 to 7.
9. SnO (stannic oxide)2Nanofiltration membrane, characterized in that the SnO2Nanofiltration membrane prepared by a process for the preparation of a filtration membrane according to any of the preceding claims 1 to 7.
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