CN109794266A - A kind of inorganic catalytic membrane and its preparation method and application - Google Patents
A kind of inorganic catalytic membrane and its preparation method and application Download PDFInfo
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- CN109794266A CN109794266A CN201910127104.1A CN201910127104A CN109794266A CN 109794266 A CN109794266 A CN 109794266A CN 201910127104 A CN201910127104 A CN 201910127104A CN 109794266 A CN109794266 A CN 109794266A
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Abstract
This application discloses a kind of inorganic catalytic membranes and its preparation method and application.The described method includes: molybdenum disulfide nano sheet is evenly dispersed in water, obtain molybdenum disulfide dispersion liquid；And the molybdenum disulfide dispersion liquid is filtered, it is deposited on molybdenum disulfide nano sheet in substrate, obtains the inorganic catalytic membrane.The better catalytic activity of the organic catalyst film of the application, persulfate can be catalyzed and generate a large amount of free radical, and pass through adjustment and control system flow field, make the quick free radical of generation and target contaminant molecule contacts and reacts, to achieve the purpose that improve free radical utilization rate, it can be used in sewage treatment.
Description
Technical field
This application involves but be not limited to water-treatment technology field, espespecially a kind of inorganic catalytic membrane and preparation method thereof and answer
With.
Background technique
China's shortage of water resources is serious, is unevenly distributed, and water pollution problems is severe.Various water treatment technologies are in water pollution control
Field played an important role.High-level oxidation technology based on persulfate is exactly one of effective ways.The method it is excellent
Gesture be the strong oxidizing property hydroxyl radical free radical generated can with non-selectivity all kinds of organic pollutants in oxygenolysis water, thus real
The purpose of existing sewage treatment.
In addition, membrane technology is due to having many advantages, such as that easy to operate, treatment effect is good, automatic control level is high, in water process
More high-quality than conventional processes, more stable outlet effect can be often obtained, so the research and application of membrane technology are gradually
Hot spot as water treatment field.It using the basic principle that membrane technology administers water pollution is carried out using the duct of film and interlamellar spacing
The separation of pollutant and water.But with the development of industrial or agricultural science and technology, organic pollutant becomes diversification, complicates, simple
Membrane separation technique is not able to satisfy existing discharge standard, and the multifunctionality of reinforced film is extremely important.
Summary of the invention
In order to solve the above-mentioned technical problem, this application provides a kind of preparation method of inorganic catalytic membrane, this method preparations
Obtained inorganic catalytic membrane has the function of that being catalyzed persulfate generates free radicals, and is not only able to as the height based on persulfate
The catalyst of grade oxidation technology is applied in sewage treatment, and enriches the functionality of film.
Specifically, this application provides a kind of preparation methods of inorganic catalytic membrane, which comprises
Molybdenum disulfide nano sheet is evenly dispersed in water, obtain molybdenum disulfide dispersion liquid；And
The molybdenum disulfide dispersion liquid is filtered, is deposited on molybdenum disulfide nano sheet in substrate, obtains the nothing
Machine catalytic membrane.
In embodiments herein, the molybdenum disulfide nano sheet can be obtained by purchase or be adopted by known method
It is prepared, for example, can be prepared using mechanical force stripping method, liquid phase ultrasonic method or lithium ion graft process etc..
In embodiments herein, the molybdenum disulfide nano sheet can lead to following methods and be prepared:
(1) hexane solution of molybdenum disulfide and organolithium is mixed in the environment of inert gas shielding, stirring setting
Time；
(2) product that step (1) obtains is washed with n-hexane, obtains the molybdenum disulfide nano sheet；
Wherein, the mass ratio of the organolithium in the hexane solution of the molybdenum disulfide and the organolithium can be 0.5
~1.5:1；
The organolithium can be n-BuLi, s-butyl lithium, any one in isobutyl group lithium and tert-butyl lithium；
The stirring can be to be heated to reflux stirring；
The setting time can be 24~72 hours, for example, can be 48 hours.
In embodiments herein, the dosage of the soft template or the hard template can be according to following selection:
The mass ratio of the iron hydroxide in molybdenum disulfide and soft template ferric hydroxide colloid in molybdenum disulfide dispersion liquid can
Think 0.5~10:1；
Molybdenum disulfide in molybdenum disulfide dispersion liquid and the silica in soft template nano silica aqueous dispersions
Mass ratio can be 5~15:1；
Molybdenum disulfide in molybdenum disulfide dispersion liquid and the zinc-oxide nano in the aqueous solution of hard template zinc oxide nanowire
The mass ratio of line can be 5~25:1；
Molybdenum disulfide in molybdenum disulfide dispersion liquid and the graphene oxide in the aqueous solution of hard template graphene oxide
Mass ratio can be 1~10:1；
Molybdenum disulfide in molybdenum disulfide dispersion liquid and the graphene quantum in the aqueous solution of hard template graphene quantum dot
The mass ratio of point can be 10~25:1.
In embodiments herein, the acid solution can be any one in hydrochloric acid, sulfuric acid, nitric acid and chloroazotic acid, institute
The mass fraction for stating acid solution can be 2~5%；The lye can be any one in sodium hydroxide and potassium hydroxide, institute
The molar concentration for stating lye can be 0.5~2mol/L.
In embodiments herein, the persulfate can be permonosulphuric acid potassium, potassium peroxydisulfate, sodium peroxydisulfate and mistake
Any one or more in ammonium sulfate.
In embodiments herein, the thickness of the molybdenum disulfide nano sheet can be 0.7~1.5nm.The thickness
Molybdenum disulfide nano sheet is easy to be evenly dispersed in water.
It is described that molybdenum disulfide nano sheet is evenly dispersed in water in embodiments herein, obtain molybdenum disulfide point
Dispersion liquid may include:
The molybdenum disulfide nano sheet is mixed with water, ultrasonic disperse；
The solution that ultrasonic disperse is obtained is centrifuged, and takes upper solution to continue to be centrifuged after centrifugation every time, until being centrifuged
To lower layer's solution in precipitation-free, being centrifuged obtained supernatant for the last time is the molybdenum disulfide dispersion liquid.
In embodiments herein, the frequency of the ultrasonic disperse can be 50~200Hz, and the time can be 30~60
Minute, temperature can be 3~7 DEG C.The frequency of 50~200Hz can be such that molybdenum disulfide nano sheet mutually removes, but not make two
Molybdenum sulfide nanometer sheet fragmentation, the phenomenon that so as to avoid molybdenum disulfide nano sheet that from can not being retained by substrate because undersized
Occur.The molybdenum disulfide nano sheet generated in ultrasonic procedure has active surface abundant and active edge, these active sites
The element sulphur set is easy to be aoxidized by oxygen (i.e. oxygen in water), and the catalytic activity for being oxidized rear molybdenum disulfide nano sheet can drop
Low, 3~7 DEG C of temperature and 30~60 minutes time substantially can inhibit oxygen in water to molybdenum disulfide nano sheet when ultrasonic
Oxidation.
In embodiments herein, the speed of the centrifugation can be 3000~7500r/min.
In embodiments herein, vacuum degree when being filtered can be -0.06~-0.1MPa.
In embodiments herein, the method can also include: after obtaining molybdenum disulfide dispersion liquid, to described
Before molybdenum disulfide dispersion liquid is filtered, the molybdenum disulfide dispersion liquid is fitted into bag filter, is dialysed in water, directly
PH to water does not change.
In embodiments herein, the method can also include:
After obtaining molybdenum disulfide dispersion liquid, before being filtered to the molybdenum disulfide dispersion liquid, bis- sulphur of Xiang Suoshu
Change in molybdenum dispersion liquid and soft template is added；And
After being filtered, the soft template in the substrate is removed with acid solution or lye.
In embodiments herein, the soft template can be ferric hydroxide colloid and nano silica aqueous dispersions
In any one or two kinds.
In embodiments herein, the method can also include:
After obtaining molybdenum disulfide dispersion liquid, before being filtered to the molybdenum disulfide dispersion liquid, bis- sulphur of Xiang Suoshu
Change in molybdenum dispersion liquid and hard template is added.
In embodiments herein, the hard template can be the aqueous solution of zinc oxide nanowire, graphene oxide
Any one or more in the aqueous solution of aqueous solution and graphene quantum dot.
In embodiments herein, the concentration of the molybdenum disulfide dispersion liquid can be 0.1~0.5mg/mL.
In embodiments herein, the substrate can be anodic alumina films, polycarbonate membrane or Kynoar
Film.
In embodiments herein, the method can also include: to filter to the molybdenum disulfide dispersion liquid
Later, the substrate for being deposited with molybdenum disulfide nano sheet obtained to suction filtration is dried, and obtains the inorganic catalytic membrane.It needs to infuse
Meaning, when the hardness of substrate is larger, for example, anodic alumina films, then be not suitable for drying, because of curing in drying process
Molybdenum film and substrate can all cause to shrink in the scale of very little because of dehydration, but anodic oxidation aluminium substrate quality is hard, almost
It will not shrink, so anodic oxidation aluminium substrate will occur the fracture of molybdenum disulfide film, be detached from after dry suction filtration molybdenum disulfide
Situations such as substrate.In addition, polycarbonate substrate, Kynoar substrate are flexible substrates, after filtering molybdenum disulfide and drying
Above-mentioned condition will not occur.
Present invention also provides a kind of inorganic catalytic membrane, the inorganic catalytic membrane is prepared by method as described above
It arrives.
Present invention also provides the applications that molybdenum disulfide film is generated free radicals as catalyst persulfate；Optionally
Ground, the molybdenum disulfide film can be inorganic catalytic membrane as described above.
Present invention also provides application of the molybdenum disulfide film in water treatment technology, comprising: consolidates to molybdenum disulfide film
It is fixed；Water to be processed is mixed with persulfate, mixed solution is made to pass through fixed molybdenum disulfide film；Optionally,
The molybdenum disulfide film can be inorganic catalytic membrane as described above.
In this application, defining " molybdenum disulfide film " is that molybdenum disulfide nano sheet deposits the film being formed on the substrate；
Defining " molybdenum disulfide film " is the membranoid substance for including molybdenum disulfide film, and molybdenum disulfide film can also include for carrying described two
Vulcanize the substrate of molybdenum film.The process that catalysis persulfate generates free radicals is limited to the activity of catalyst.In addition, generate from
It is extremely short by the base service life, if utilized not in time, free radical will self-quenching at non-oxidation ability water.Therefore, one it is efficient
The process that removal organic polluter is removed using free radical should include two parts: first, system produces a large amount of free radical, freely
Base is the core of oxidation of organic compounds, and a large amount of free radical can resist negative effect caused by self-quenching to a certain extent, into
And keep the organic pollutant removal rate of more efficient；Second, efficiently utilize the free radical produced.The organic catalyst of the application
The better catalytic activity of film can be catalyzed persulfate and generate a large amount of free radical, and by adjustment and control system flow field, make to generate
Free radical quickly and target contaminant molecule contacts and react, to achieve the purpose that raising free radical utilization rate.
Other features and advantage will illustrate in the following description, also, partly become from specification
It obtains it is clear that being understood and implementing the application.The purpose of the application and other advantages can be by specifications, right
Specifically noted structure is achieved and obtained in claim and attached drawing.
Detailed description of the invention
Attached drawing is used to provide to further understand technical scheme, and constitutes part of specification, with this
The embodiment of application is used to explain the technical solution of the application together, does not constitute the limitation to technical scheme.
Fig. 1 is the application effect figure of the inorganic catalytic membrane of the embodiment of the present application 4；
Fig. 2 is the application effect figure of the inorganic catalytic membrane of the embodiment of the present application 5；
Fig. 3 is the electron paramagnetic resonance map of the catalyst system of the embodiment of the present application 4；
Fig. 4 is that the catalyst system of the embodiment of the present application generates free radicals and remove bisphenol-A under the action of itself micro flow field
Schematic diagram.
Specific embodiment
For the purposes, technical schemes and advantages of the application are more clearly understood, below in conjunction with attached drawing to the application
Embodiment be described in detail.It should be noted that in the absence of conflict, in the embodiment and embodiment in the application
Feature can mutual any combination.
Raw materials and reagents employed in following embodiment are unless otherwise instructed ordinary commercial products.
The preparation embodiment of inorganic catalytic membrane
Embodiment 1
The preparation method of the inorganic catalytic membrane of the present embodiment includes:
(1) by the hexane solution of 300mg commodity class molybdenum disulfide and 3mL n-BuLi, (quality of n-BuLi is
It 450mg) mixes in the glove box of argon gas protection, and persistently stirs 48 hours under the protection of argon gas；
(2) product that step (1) obtains is washed with 100mL n-hexane, to remove extra n-BuLi, obtains thickness
The about molybdenum disulfide nano sheet of 1.5nm；
(3) the rapid ultrasonic disperse of molybdenum disulfide nano sheet for obtaining step (2) is in 100mL deionized water, and at 3 DEG C
Low temperature water-bath in continual ultrasonic 60 minutes, ultrasonic frequency be 50Hz；
(4) solution that step (3) obtains is centrifuged according to the following steps (note that the sediment of all centrifugation steps is all abandoned
Go), after being centrifuged 30 minutes with the speed of 3000r/min first, takes out upper solution and be centrifuged it with the speed of 4500r/min
It 10 minutes, further takes out upper solution and is centrifuged 10 minutes with the speed of 7500r/min, substantially without heavy in centrifuge tube after centrifugation
It forms sediment, the supernatant after taking last time to be centrifuged, as molybdenum disulfide dispersion liquid, concentration are 0.1mg/mL (molybdenum disulfide dispersion
The concentration of liquid is tested using gravimetric method: it is accurate to measure 50mL molybdenum disulfide dispersion liquid, it is lyophilized to constant weight, weighs black lyophilized products
Quality obtains the mass concentration of molybdenum disulfide dispersion liquid after calculating)；
(5) the molybdenum disulfide dispersion liquid is fitted into the bag filter of 3000Da, is dialysed in deionized water to deionization
Until the pH of water is constant；
(6) it is filtered by vacuum with the molybdenum disulfide dispersion liquid that anodic alumina films obtain 35mL step (5), vacuum is taken out
The vacuum degree of filter is -0.06Mpa.
The overall thickness for the inorganic catalytic membrane that the present embodiment is prepared is about 100 μm, molybdenum disulfide film therein it is straight
Diameter is about 4cm, and the quality of the molybdenum disulfide in molybdenum disulfide dispersion liquid filtered in step (6) (is deposited on two in substrate
The quality of molybdenum sulfide) it is about 3.5mg, rule of thumb, in the case where template is not added, the thickness that 1mg molybdenum disulfide corresponds to film is
100nm can deduce that the thickness of the molybdenum disulfide film in inorganic catalytic membrane is about 350nm.
Embodiment 2
The preparation method of the inorganic catalytic membrane of the present embodiment includes:
(1) by the hexane solution of 300mg commodity class molybdenum disulfide and 3mL isobutyl group lithium, (quality of isobutyl group lithium is
It 450mg) mixes in the glove box of argon gas protection, and persistently stirs 48 hours under the protection of argon gas；
(2) product that step (1) obtains is washed with 50mL n-hexane, to remove extra isobutyl group lithium, obtains thickness
The about molybdenum disulfide nano sheet of 1.5nm；
(3) the rapid ultrasonic disperse of molybdenum disulfide nano sheet for obtaining step (2) is in 100mL deionized water, and at 5 DEG C
Low temperature water-bath in continual ultrasonic 60 minutes, ultrasonic frequency be 200Hz；
(4) solution that step (3) obtains is centrifuged according to the following steps (note that the sediment of all centrifugation steps is all abandoned
Go), after being centrifuged 30 minutes with the speed of 3000r/min first, takes out upper solution and be centrifuged it with the speed of 4500r/min
It 10 minutes, further takes out upper solution and is centrifuged 10 minutes with the speed of 7500r/min, substantially without heavy in centrifuge tube after centrifugation
It forms sediment, the supernatant after taking last time to be centrifuged, as molybdenum disulfide dispersion liquid, concentration 0.5mg/mL；
(5) the molybdenum disulfide dispersion liquid is fitted into the bag filter of 3000Da, is dialysed in deionized water to deionization
Until the pH of water is constant；
(6) 1ml soft template ferric hydroxide colloid is added in the molybdenum disulfide dispersion liquid for taking 15ml step (5) to obtain thereto
(the about 8mg containing iron hydroxide) is filtered by vacuum obtained mixed liquor with polyvinylidene fluoride film, after draining film forming, continues to use
The HCl of 20mL 2wt% carries out suction filtration etching, after HCl is drained, 20mL deionized water is added and continues filtering and washing；Wherein, hydrogen
The preparation method of colloid of iron oxide are as follows: the liquor ferri trichloridi of 0.4mL is added dropwise in the deionized water boiled to 200 milliliters (by 5g
FeCl3It is dissolved in 8mL H2Obtained in O), it is further continued for boiling 5 minutes after adding, it is stand-by after cooling；The vacuum degree of vacuum filtration be-
0.08MPa；
(7) formation for obtaining step (6) has the polyvinylidene fluoride film of molybdenum disulfide film drying 12 hours at 40 DEG C,
Obtain the inorganic catalytic membrane.
The overall thickness for the inorganic catalytic membrane that the present embodiment is prepared is 125 μm, the thickness of molybdenum disulfide film therein
It is 1 μm.
Embodiment 3
The preparation method of the inorganic catalytic membrane of the present embodiment includes:
(1) by the hexane solution of 300mg commodity class molybdenum disulfide and 3mL tert-butyl lithium, (quality of tert-butyl lithium is
It 450mg) mixes in the glove box of argon gas protection, and persistently stirs 48 hours under the protection of argon gas；
(2) product that step (1) obtains is washed with 150mL n-hexane, to remove extra tert-butyl lithium, obtains thickness
The about molybdenum disulfide nano sheet of 1.5nm；
(3) the rapid ultrasonic disperse of molybdenum disulfide nano sheet for obtaining step (2) is in 100mL deionized water, and at 7 DEG C
Low temperature water-bath in continual ultrasonic 60 minutes, ultrasonic frequency be 100Hz；
(4) solution that step (3) obtains is centrifuged according to the following steps (note that the sediment of all centrifugation steps is all abandoned
Go), after being centrifuged 30 minutes with the speed of 3000r/min first, takes out upper solution and be centrifuged it with the speed of 4500r/min
It 10 minutes, further takes out upper solution and is centrifuged 10 minutes with the speed of 7500r/min, substantially without heavy in centrifuge tube after centrifugation
It forms sediment, the supernatant after taking last time to be centrifuged, as molybdenum disulfide dispersion liquid, concentration 0.2mg/mL；
(5) the molybdenum disulfide dispersion liquid is fitted into the bag filter of 3000Da, is dialysed in deionized water to deionization
Until the pH of water is constant；
(6) 5ml hard template zinc oxide nanowire is added in the molybdenum disulfide dispersion liquid for taking 25ml step (5) to obtain thereto
Aqueous solution (the about 0.25mg containing zinc oxide nanowire), then obtained mixed liquor is filtered by vacuum with polycarbonate membrane；
Wherein, the preparation method of the aqueous solution of zinc oxide nanowire are as follows: weighing 5.0mg commerical grade zinc oxide nanowire, (nanowire diameter is about
10~50nm, length are about 1~20 μm) (ultrasonic frequency is 200Hz, time 30 to ultrasonic disperse in 100mL deionized water
Minute)；The vacuum degree of vacuum filtration is -0.1MPa；
(7) formation for obtaining step (6) has the polycarbonate membrane of molybdenum disulfide film 12 hours dry at 40 DEG C, obtains
To the inorganic catalytic membrane.
The overall thickness for the inorganic catalytic membrane that the present embodiment is prepared is about 100 μm, the thickness of molybdenum disulfide film therein
Degree is about 500nm.
The Application Example of inorganic catalytic membrane
Embodiment 4
By inorganic catalytic membrane prepared by embodiment 1 be put into stainless steel change membrane filter (Millipore, XX4404700,
Blending bolt is fixed in 47mm), the mixed aqueous solution of addition 4 liters of bisphenol-As and potassium hydrogen persulfate into pressure water tank, double in solution
The concentration of phenol A (BPA) is 5mg/L, and the concentration of potassium hydrogen persulfate is 100mg/L；The then pressure water tank and nitrogen of connection front end
Nitrogen cylinder is opened after beaker for holding water outlet is arranged in rear end in source, adjusts the pressure of nitrogen to 0.2bar (about 0.2 times of mark
Quasi- atmospheric pressure), start timing when the water outlet of rear end flows out the first drop of liquid, spot sampling, bisphenol-A is dense in measurement water outlet
It spends and records water outlet volume.Experimental result is as shown in Figure 1.
As can be seen that the flux of the inorganic catalytic membrane was held essentially constant, bisphenol-A by 360 minutes continuous experiments
Removal rate is consistently higher than 90%, illustrates that the inorganic catalytic membrane has good catalytic activity and stability.
Embodiment 5
By inorganic catalytic membrane prepared by embodiment 2 be put into stainless steel change membrane filter (Millipore, XX4404700,
Blending bolt is fixed in 47mm), the mixed aqueous solution of addition 4 liters of bisphenol-As and potassium hydrogen persulfate into pressure water tank, double in solution
The concentration of phenol A (BPA) is 5mg/L, and the concentration of potassium hydrogen persulfate is 100mg/L；The then pressure water tank and nitrogen of connection front end
Nitrogen cylinder is opened after beaker for holding water outlet is arranged in rear end in source, adjusts the pressure of nitrogen to 0.2bar (about 0.2 times of mark
Quasi- atmospheric pressure), start timing when the water outlet of rear end flows out the first drop of liquid, spot sampling, bisphenol-A is dense in measurement water outlet
It spends and records water outlet volume.Experimental result is as shown in Figure 2.
As can be seen that the flux of the inorganic catalytic membrane generally changed less, bisphenol-A by 360 minutes continuous experiments
Removal rate be consistently higher than 90%, it should be noted that the molybdenum disulfide film in embodiment 2 be added mantle plate after pickling obtain
It arrives, the interlamellar spacing of the film slightly increases compared to the film in embodiment 1, therefore embodiment 5 shows as leading in experimental result
It measures higher.The result of embodiment 5 illustrates that the inorganic catalytic membrane has good catalytic activity and stability, while also having higher
Flux.
Molybdenum disulfide catalysis persulfate generates free radicals, and the free radical of these strong oxidizing properties is the oxidation of degradation bisphenol-A
Active specy can prove that the catalyst system mainly produces hydroxyl radical free radical by electron paramagnetic resonance, adopt in embodiment 4
The electron paramagnetic resonance map of catalyst system is as shown in Fig. 3.As can be seen that in 3481G, 3500G, 3511G and 3526G
The 4 weight peaks occurred are the characteristic peaks of hydroxyl radical free radical.It should be appreciated that the inorganic catalytic membrane of other embodiments is formed with persulfate
Catalyst system can produce the characteristic peak of hydroxyl radical free radical, no longer list its electron paramagnetic resonance map one by one herein.
While not wishing to be bound by theory, but present inventor analyzes the formation of the inorganic catalytic membrane of the application
And catalysis are as follows: the thickness using the molybdenum disulfide lamella of organolithium removing is about 1.5nm, is filtering molybdenum disulfide point
During dispersion liquid, these lamellas stack film forming, and the interlamellar spacing inside film is approximately 1.2nm.If be added during suction filtration
Template (soft template or hard template), then can increase interlamellar spacing, the flux of adjusting film to a certain extent, and enhancing water is received inside film
Disturbance in rice structure；Special construction inside film results in the hydrodynamics different from beaker system, and the water for flowing through film is abundant
The internal nanostructure of contact membranes, the hydrodynamics in this micro flow field improve the mass-transfer efficiency of substance, and this point is conducive to
The promotion of Chemical Kinetics.Specific micro flow field schematic diagram is as shown in figure 4, the h in Fig. 4 indicates the thickness of molybdenum disulfide film
Degree, h1Indicate the thickness of molybdenum disulfide nano sheet, h2Indicate interlamellar spacing inside film layer (the reason of it is micro flow field formation), h2About
For 1.2~1.8nm.In micro flow field, the persulfate in solution is cracked into rapidly hydroxyl radical free radical on molybdenum disulfide surface, by
In liquid confinement in the section of nanoscale, the diffusion that the free radical of generation can not need long range can be with pair in water
Phenol A molecule contacts, benefit that there are two this processes, first, persulfate highly effective reaction generates a large amount of free radicals；Second, it is ultrashort
The mass transfer of distance greatly improves the contact and reaction of strong oxidizing property free radical with organic contamination molecule (bisphenol-A) in water, overcomes
The shortcomings that beaker system long range mass transfer.Therefore, in water treatment technology, when select the inorganic catalytic membrane of the application as urging
When agent catalysis persulfate generates free radicals, good organic pollutant removal effect can be obtained.
Although embodiment disclosed by the application is as above, the content only for ease of understanding the application and use
Embodiment is not limited to the application.Technical staff in any the application fields, is taken off not departing from the application
Under the premise of the spirit and scope of dew, any modification and variation, but the application can be carried out in the form and details of implementation
Scope of patent protection, still should be subject to the scope of the claims as defined in the appended claims.
Claims (10)
1. a kind of preparation method of inorganic catalytic membrane, which is characterized in that the described method includes:
Molybdenum disulfide nano sheet is evenly dispersed in water, obtain molybdenum disulfide dispersion liquid；And
The molybdenum disulfide dispersion liquid is filtered, is deposited on molybdenum disulfide nano sheet in substrate, obtains described inorganic urge
Change film.
2. it is described that molybdenum disulfide nano sheet is evenly dispersed in water according to the method described in claim 1, wherein, obtain two
Molybdenum sulfide dispersion liquid includes:
The molybdenum disulfide nano sheet is mixed with water, ultrasonic disperse；
The solution that ultrasonic disperse is obtained is centrifuged, and takes upper solution to continue to be centrifuged after centrifugation every time, until what centrifugation obtained
Precipitation-free in lower layer's solution, being centrifuged obtained supernatant for the last time is the molybdenum disulfide dispersion liquid；
Optionally, the frequency of the ultrasonic disperse is 50~200Hz, and the time is 30~60 minutes, and temperature is 3~7 DEG C；It is described from
The speed of the heart is 3000~7500r/min；
Optionally, vacuum degree when being filtered is -0.06~-0.1MPa.
3. according to the method described in claim 1, further include: after obtaining molybdenum disulfide dispersion liquid, to the molybdenum disulfide
Before dispersion liquid is filtered, the molybdenum disulfide dispersion liquid is fitted into bag filter, is dialysed in water, until the pH of water
It does not change.
4. according to the method described in claim 1, further include:
After obtaining molybdenum disulfide dispersion liquid, before being filtered to the molybdenum disulfide dispersion liquid, Xiang Suoshu molybdenum disulfide
Soft template is added in dispersion liquid；And
After being filtered, the soft template in the substrate is removed with acid solution or lye；
Optionally, the soft template is any one in ferric hydroxide colloid and nano silica aqueous dispersions or two kinds.
5. according to the method described in claim 1, further include:
After obtaining molybdenum disulfide dispersion liquid, before being filtered to the molybdenum disulfide dispersion liquid, Xiang Suoshu molybdenum disulfide
Hard template is added in dispersion liquid；
Optionally, the hard template is the aqueous solution and graphene quantum dot of the aqueous solution of zinc oxide nanowire, graphene oxide
Aqueous solution in any one or more.
6. method according to any one of claims 1-5, wherein the concentration of the molybdenum disulfide dispersion liquid be 0.1~
0.5mg/mL。
7. method according to any one of claims 1-5, wherein the substrate is anodic alumina films, polycarbonate
Film or polyvinylidene fluoride film.
8. a kind of inorganic catalytic membrane, the inorganic catalytic membrane is prepared by method of any of claims 1-7.
9. the application that molybdenum disulfide film is generated free radicals as catalyst persulfate；Optionally, the molybdenum disulfide film
For inorganic catalytic membrane according to any one of claims 8.
10. application of the molybdenum disulfide film in water treatment technology, comprising: molybdenum disulfide film is fixed；By water to be processed
It is mixed with persulfate, mixed solution is made to pass through fixed molybdenum disulfide film；
Optionally, the molybdenum disulfide film is inorganic catalytic membrane according to any one of claims 8.
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| CN110180564A (en) * | 2019-06-19 | 2019-08-30 | 清华大学 | A kind of molybdenum disulfide catalytic membrane and its preparation and application |
| CN113117749A (en) * | 2021-04-21 | 2021-07-16 | 宁夏大学 | Preparation method and application of composite catalytic membrane for catalytically removing COD (chemical oxygen demand) in high-salt-content wastewater in coal chemical industry |
| CN113135594A (en) * | 2020-01-19 | 2021-07-20 | 广东工业大学 | Persulfate activation method and application thereof |
| CN113289657A (en) * | 2021-05-21 | 2021-08-24 | 山西大学 | Preparation method and application of nitrogen-doped graphene catalytic membrane |
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