CN107308948A - The preparation method and application of multi-level nano-structure flexible inorganic film - Google Patents

The preparation method and application of multi-level nano-structure flexible inorganic film Download PDF

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CN107308948A
CN107308948A CN201710571526.9A CN201710571526A CN107308948A CN 107308948 A CN107308948 A CN 107308948A CN 201710571526 A CN201710571526 A CN 201710571526A CN 107308948 A CN107308948 A CN 107308948A
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manganese dioxide
membrane
dioxide nanowire
temperature
deionized water
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CN107308948B (en
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梁恒
罗鑫圣
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
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    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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    • C01—INORGANIC CHEMISTRY
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Abstract

The preparation method and application of multi-level nano-structure flexible inorganic film, is related to a kind of preparation method and application of flexible inorganic film.Be to solve it is existing catalysis peroxy-monosulfate powdered nanocatalyst catalytic efficiency it is low, it is necessary to further reclaim, more bother the problem of.Method：First, flexible manganese dioxide film substrate is prepared；2nd, multi-level nano-structure catalytic membrane is prepared.Application of the multi-level nano-structure flexible inorganic film in catalysis peroxy-monosulfate.The catalytic membrane is effectively improved catalytic oxidation efficiency, so that peroxy-monosulfate is highly efficient, thorough to the degradation of organic pollution, inorganic catalytic membrane when being filtering due to being catalyzed, therefore without further reclaiming after use, and service life is long, it can be used untill in itself breakage occurs for film.The present invention is used for sewage treatment area.

Description

The preparation method and application of multi-level nano-structure flexible inorganic film
Technical field
The present invention relates to a kind of preparation method and application of flexible inorganic film.
Background technology
High-level oxidation technology is one kind by outside energy (luminous energy, heat energy, ultrasonic wave good fortune are penetrated or microwave good fortune is penetrated) or urged The introducing of agent reaches activation H2O2Or O3Deng the purpose of Green Oxidant, the active group produced in activation process such as hydroxyl is utilized Base free radical (OH) or potentiometric titrations (SO4-) organic pollution degrade and mineralising oxidation technology.Initially The high-level oxidation technology of proposition refers in particular to think the oxidation technology of active oxidation species, generally includes Fenton oxidation technology, light and urges Change technology, Ultrasonic Irradiation, ozonation technology, persulfate active oxidation technology etc..In these high-level oxidation technologies, Persulfate persulfate can be applied to the reparation by the underground water of Organic Pollution and soil, in recent years, external neck new herein There is faster development in domain.Therefore, the SO produced is activated using persulfate4·-It is new that degradable organic pollutant is turning into a class High-level oxidation technology.Persulfate includes peroxydisulfate (S2O8 2-) and peroxy-monosulfate (HSO5-), wherein peroxy-disulfuric acid Salt existence form mainly has sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate.The underground water and soil polluted in organic pollution In reparation, generally using sodium peroxydisulfate (the 78g/100g H with highly-water-soluble2O,25℃).Peroxy-monosulfate it is main with 2KHSO5·KHSO4·K2SO4The form of three salt compounds is present, trade name Oxone.Wherein active material is single peroxide sulphur Sour oxygen potassium.Persulfuric acid salt form high-level oxidation technology has that oxidant stability is good, dissolubility is good, and activation method is more, and pH is applicable anti- The advantages of Ying Guang, strong anti-inorganic salts interference performance, and the SO produced4·-(half-life period in life-span is 4s) (life-span is less than 1 than OH μ s) it is long, be conducive to contact with pollutant, increase chance of the free radical to contaminant degradation.Therefore, with SO4·-Based on High-level oxidation technology, the high-level oxidation technology as great development prospect.
The catalytic reaction of advanced oxidation reaction under current ambient temperature normal pressure typically distinguishes homogeneous catalysis and heterogeneous catalysis two Major class.Homogeneous catalytic reaction is usually using metal ion as catalyst.But be due to catalyst easy in inactivation in homogeneous catalytic reaction, Easily into salt slurry, separation is difficult, easily cause secondary pollution the shortcomings of, just gradually replaced by heterogeneous catalysis.
With continuing to develop for nanometer technology, function nano material due to bigger serface and high catalytic activity by It is widely used in catalytic field.However, nano-catalyst particles, which are often reunited and form bulky grain material, causes its catalytic activity Reduction, catalytic efficiency is not high, and with methylene blue example, 0.5~1 hour is at least needed using powder catalyst catalysis methylene blue The degradation rate of methylene blue can be made to reach more than 90%.
In addition, also needing to further recovery, cumbersome, service life in powdered nanocatalyst running It is shorter.
The content of the invention
The present invention is to solve the powdered nanocatalyst catalytic efficiency of existing catalysis peroxy-monosulfate is low, it is necessary to enter one Step is reclaimed, and there is provided the preparation method and application of multi-level nano-structure flexible inorganic film for the problem of more bothering.
The preparation method of multi-level nano-structure flexible inorganic film of the present invention, comprises the following steps：
First, flexible manganese dioxide film substrate is prepared：
The preparation method of the flexible manganese dioxide film substrate is method one, method two or method three；
Method one is：
Potassium permanganate and ammonium chloride are dissolved in deionized water, stirred 1~2 hour；
The solution stirred is poured into hydrothermal reaction kettle, reacted 12~36 hours under conditions of 160~220 DEG C；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, in 65~70 DEG C of temperature Degree is lower to dry 10~12h, obtains manganese dioxide nanowire；
According to required film thickness and diameter, manganese dioxide nanowire is taken, manganese dioxide nanowire ultrasonic disperse is existed In distilled water, filtered, dried 30~40 minutes at a temperature of 65~70 DEG C, the shape on filter membrane with 0.45 micron of glass fiber filter Into manganese dioxide nanowire membrane, soft manganese dioxide nanowire membrane is peeled above filter membrane, 0.45 micron of glass fibers Tie up filter membrane reusable；
By manganese dioxide nanowire membrane at a temperature of 400~600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire Film.
Wherein the mass ratio of potassium permanganate, ammonium chloride and deionized water is (0.1~0.5)：(0.4~3.4)：100
Method two is：
Potassium permanganate is dissolved in deionized water, ethyl acetate is added, under conditions of 85~95 DEG C return stirring 2~ 3 days；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, in 65~70 DEG C of temperature Degree is lower to dry 10~12h, obtains manganese dioxide nanowire；
According to required film thickness and diameter, manganese dioxide nanowire is taken, manganese dioxide nanowire ultrasonic disperse is existed In distilled water, filtered, dried 30~40 minutes at a temperature of 65~70 DEG C, the shape on filter membrane with 0.45 micron of glass fiber filter Into manganese dioxide nanowire membrane, soft manganese dioxide nanowire membrane is peeled above filter membrane, 0.45 micron of glass fibers Tie up filter membrane reusable；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire Film.
Wherein the mass ratio of potassium permanganate, ethyl acetate and deionized water is (1.2~3.5)：(89~267)：750
Method three is：
Manganese sulfate, potassium chlorate and potassium acetate are dissolved in deionized water, stirred 30~40 minutes；
The solution stirred is poured into hydrothermal reaction kettle, reacted 6~12 hours under conditions of 160~180 DEG C；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, in 65~70 DEG C of temperature Degree is lower to dry 10~12h, obtains manganese dioxide nanowire；
According to required film thickness and diameter, manganese dioxide nanowire is taken, manganese dioxide nanowire ultrasonic disperse is existed In distilled water, filtered, dried 30~40 minutes at a temperature of 65~70 DEG C, the shape on filter membrane with 0.45 micron of glass fiber filter Into manganese dioxide nanowire membrane, soft manganese dioxide nanowire membrane is peeled above filter membrane, 0.45 micron of glass fibers Tie up filter membrane reusable；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire Film.
Wherein the mass ratio of manganese sulfate, potassium chlorate, potassium acetate and deionized water is (1.2~3.6)：(0.8~3.2)： (0.63~3.7)：100.
2nd, multi-level nano-structure catalytic membrane is prepared：
The preparation method of the multi-level nano-structure catalytic membrane is method one or method two；
Method one：
The manganese dioxide nanowire membrane prepared is taken, the mixed solution of 0.05~0.1mol/L copper acetates and ethanol is soaked in In, drying is taken out after 10~15s of immersion, after repeating 3~5 times, is put into Muffle furnace and is calcined 20~60 minutes at 200~400 DEG C.
Copper nitrate is dissolved in deionized water, ammoniacal liquor is added and stirs, obtain the mixed solution of copper nitrate and ammoniacal liquor；Its The mass ratio of middle copper nitrate, ammoniacal liquor and deionized water is (0.01~0.2)：(0.9~2.7)：100.
Manganese dioxide nanowire membrane after will be calcined is put into the mixed solution of copper nitrate and ammoniacal liquor, stands 12~48 small When after obtain manganese oxide nano wire/cupric oxide nano piece multi-level nano-structure catalytic membrane.
Method two：
The manganese dioxide nanowire membrane prepared is taken, the mixed solution of 0.05~0.1mol/L copper acetates and ethanol is soaked in In, drying is taken out after 10~15s of immersion, after repeating 3~5 times, is put into Muffle furnace and is calcined 20~60 minutes at 200~400 DEG C.
Copper nitrate is dissolved in deionized water, hexamethylenetetramine is added and stirs, obtain mixed solution；Wherein nitric acid The mass ratio of copper, hexamethylenetetramine and deionized water is (0.01~0.2)：(0.14~1.2)：100.
Manganese dioxide nanowire membrane after will be calcined is put into mixed solution, stands 30~40 minutes, then 85~ 92 DEG C of hydro-thermal process 6~12 hours, obtain the catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano line.
The application of multi-level nano-structure flexible inorganic film prepared by the above method in catalysis peroxy-monosulfate.
Specific method is：By peroxy-monosulfate and treat degradation of contaminant mix, then using level nanostructured flexible inorganic Film is filtered to mixture.It is described to treat that degradation of contaminant is methylene blue, Atrazine, p-nitrophenol or sulfanilamide (SN) dimethyl Pyrimidine, but it is not limited only to these pollutants.
The invention has the advantages that：
(1) the invention provides a kind of flexible inorganic film with peroxy-monosulfate catalysis, flexible operation mode, behaviour Make method simple, raw material needed for preparing is easier to obtain.
(2) inorganic catalytic membrane with multi-level nano-structure for preparing of the present invention, because for nanoscale structures, its surface is thick Rough injustice, therefore the specific surface area of film is improved, by 19cm2/ g brings up to 44cm2/g.And then mass-transfer efficiency is added, effectively Improve catalytic oxidation efficiency so that peroxy-monosulfate is highly efficient, thorough to the degradation of organic pollution, obtain More preferable effluent quality.Exemplified by using methylene blue (MB) as model pollutant, activated using the inorganic catalytic membrane of the present invention One sulfate degradation of contaminant methylene blue, is specifically to mix peroxy-monosulfate with pollutant, then using the nothing of the present invention Machine catalytic membrane is filtered, and is that activation peroxy-monosulfate produces free radical while filtering, to methylene blue (0.1mmol/L) Clearance can reach 98.1%~99.8%.Catalytic process moment completes, and catalytic efficiency is efficient, according to first order kinetics (formula 1) calculate, catalytic membrane activation PMS degradeds MB observed rate constant is k '=24.6, far above typical catalyst.
C in formula 10And ClConcentration respectively after MB initial concentration and filtering degraded.L is the thickness of film, and v is in film Fluid linear velocity, t ' is time of contact in film, and k ' is first order kinetics observed rate constant.
Peroxy-monosulfate is activated and methylene blue degradation principles are as follows：
≡CuII-OH+HSO5 -→≡CuII-(O)OSO3 -+H2O
≡CuI-OH+HSO5 -→≡CuI-(O)OSO3 -+H2O
≡MnIV-OH+HSO5 -→≡MnIV-(O)OSO3 -+H2O
≡MnIII-OH+HSO5 -→≡MnIII-(O)OSO3 -+H2O
(3) inorganic catalytic membrane of multi-level nano-structure prepared by the present invention, the multistage with manganese dioxide and cupric oxide is received Rice structure, can fully play manganese dioxide and oxidation copper compound is urged the absorption of organic pollution and the collaboration of peroxy-monosulfate Change degradation, making the catalytic membrane of preparation has the multiple actions such as absorption, peroxy-monosulfate catalysis oxidation and membrane filtration, realizes It is multi-functional integrated.Peroxy-monosulfate itself has the efficiency of degradation of contaminant as oxidant, but due to its oxidative degradation speed Rate is slower, so generally requiring activation produces free radical, accelerates degradation rate.Manganese dioxide and cupric oxide do not aoxidize drop in itself The efficiency of organic matter is solved, as catalyst, catalytic activation peroxy-monosulfate produces free radical.
(4) inorganic catalytic membrane of the invention when being filtering due to being catalyzed, therefore need not further be reclaimed after use, and And service life is long, it can be used untill in itself breakage occurs for film.Present invention is mainly applied to drinking water and chemical wastewater treatment.
Brief description of the drawings
Fig. 1 is the pictorial diagram of catalytic membrane prepared by embodiment 1；
Fig. 2 is the scanning electron microscope diagram of catalytic membrane prepared by embodiment 1；
Fig. 3 is the X-ray diffraction spectrogram of catalytic membrane prepared by embodiment 1.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment Any combination.
Embodiment one：The preparation method of present embodiment multi-level nano-structure flexible inorganic film, including following step Suddenly：
First, flexible manganese dioxide film substrate is prepared：
The preparation method of the flexible manganese dioxide film substrate is method one, method two or method three；
Method one is：
Potassium permanganate and ammonium chloride are dissolved in deionized water, stirred 1~2 hour；
The solution stirred is poured into hydrothermal reaction kettle, reacted 12~36 hours under conditions of 160~220 DEG C；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, in 65~70 DEG C of temperature Degree is lower to dry 10~12h, obtains manganese dioxide nanowire；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~ Dried 30~40 minutes at a temperature of 70 DEG C, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire Film is peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400~600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire Film；
Method two is：
Potassium permanganate is dissolved in deionized water, ethyl acetate is added, under conditions of 85~95 DEG C return stirring 2~ 3 days；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, in 65~70 DEG C of temperature Degree is lower to dry 10~12h, obtains manganese dioxide nanowire；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~ Dried 30~40 minutes at a temperature of 70 DEG C, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire Film is peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire Film；
Method three is：
Manganese sulfate, potassium chlorate and potassium acetate are dissolved in deionized water, stirred 30~40 minutes；
The solution stirred is poured into hydrothermal reaction kettle, reacted 6~12 hours under conditions of 160~180 DEG C；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, in 65~70 DEG C of temperature Degree is lower to dry 10~12h, obtains manganese dioxide nanowire；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~ Dried 30~40 minutes at a temperature of 70 DEG C, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire Film is peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire Film；
2nd, multi-level nano-structure catalytic membrane is prepared：
The preparation method of the multi-level nano-structure catalytic membrane is method one or method two；
Method one：
The manganese dioxide nanowire membrane prepared is taken, the mixed solution of 0.05~0.1mol/L copper acetates and ethanol is soaked in In, drying is taken out after 10~15s of immersion, after repeating 3~5 times, is put into Muffle furnace and is calcined 20~60 minutes at 200~400 DEG C；
Copper nitrate is dissolved in deionized water, ammoniacal liquor is added and stirs, obtain the mixed solution of copper nitrate and ammoniacal liquor；
Manganese dioxide nanowire membrane after will be calcined is put into the mixed solution of copper nitrate and ammoniacal liquor, stands 12~48 small When after obtain manganese oxide nano wire/cupric oxide nano piece multi-level nano-structure catalytic membrane；
Method two：
The manganese dioxide nanowire membrane prepared is taken, the mixed solution of 0.05~0.1mol/L copper acetates and ethanol is soaked in In, drying is taken out after 10~15s of immersion, after repeating 3~5 times, is put into Muffle furnace and is calcined 20~60 minutes at 200~400 DEG C；
Copper nitrate is dissolved in deionized water, hexamethylenetetramine is added and stirs, obtain mixed solution；
Manganese dioxide nanowire membrane after will be calcined is put into mixed solution, stands 30~40 minutes, then 85~ 92 DEG C of hydro-thermal process 6~12 hours, obtain the catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano line.
Embodiment two：Present embodiment from unlike embodiment one：It is high in the method one of step one The mass ratio of potassium manganate, ammonium chloride and deionized water is (0.1~0.5)：(0.4~3.4)：100.Other and embodiment One is identical.
Embodiment three：Present embodiment from unlike embodiment one or two：The method two of step one The mass ratio of middle potassium permanganate, ethyl acetate and deionized water is (1.2~3.5)：(89~267)：750.Other and specific reality Apply mode one or two identical.
Embodiment four：Unlike one of present embodiment and embodiment one to three：The side of step one Manganese sulfate in method three, potassium chlorate, the mass ratio of potassium acetate and deionized water are (1.2~3.6)：(0.8~3.2)：(0.63~ 3.7)：100.It is other identical with one of embodiment one to three.
Embodiment five：Unlike one of present embodiment and embodiment one to four：The side of step 2 The mass ratio of copper nitrate, ammoniacal liquor and deionized water is (0.01~0.2) in method one：(0.9~2.7)：100.Other and specific reality Apply one of mode one to four identical.
Embodiment six：Unlike one of present embodiment and embodiment one to five：The side of step 2 The mass ratio of copper nitrate, hexamethylenetetramine and deionized water is (0.01~0.2) in method two：(0.14~1.2)：100.It is other It is identical with one of embodiment one to five.
Embodiment seven：Present embodiment multi-level nano-structure flexible inorganic film answering in catalysis peroxy-monosulfate With.
Embodiment eight：Present embodiment from unlike embodiment seven：It is soft using multi-level nano-structure The specific method of the inorganic Membrane catalysis peroxy-monosulfate of property is：By peroxy-monosulfate and treat degradation of contaminant mix, then using level Nanostructured flexible inorganic film is filtered to mixture.It is other identical with embodiment seven.
Embodiment nine：Present embodiment from unlike embodiment eight：It is described to treat that degradation of contaminant is Methylene blue, Atrazine, p-nitrophenol or sulfamethazine.It is other identical with embodiment eight.
Embodiments of the invention are elaborated below, following examples are entered under premised on technical solution of the present invention Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities Apply example.
Embodiment 1：
First, flexible manganese dioxide film matrix is prepared
1) 0.1g potassium permanganate and 0.6g ammonium chloride are dissolved in 100mL deionized waters, are stirred 1 hour；
2) solution stirred is poured into 200mL hydrothermal reaction kettles, reacted 12 hours under conditions of 160 DEG C；
3) after reaction terminates, resulting sediment is filtered on 0.45 micron of glass fiber filter, in 65 DEG C of temperature Degree is lower to dry 12h, obtains manganese dioxide nanowire；
4) 50mg manganese dioxide nanowires are taken, using ultrasonic disperse in the 100mL aqueous solution, the filter at 0.45 micron are filtered On film, dry 30 minutes, easily can take soft manganese dioxide nanowire membrane above filter membrane off at a temperature of 65 DEG C Come, 0.45 micron of filter membrane is reusable；
5) the high-temperature roasting 1h at a temperature of 450 DEG C, obtains manganese dioxide nanowire membrane.
2nd, multi-level nano-structure catalytic membrane is prepared
1) take in the manganese dioxide film prepared, the mixed solution for being soaked in 5mmol/L copper acetates and ethanol, soak 15 seconds Take out afterwards after drying, repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.2g copper nitrates are dissolved in 100mL deionized waters, add 1.8mL ammoniacal liquor and stir；
3) the manganese dioxide film after will be calcined is put into the mixed solution of copper nitrate and ammoniacal liquor, is obtained after standing 6 hours The catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano piece.
Experiment effect：
By peroxy-monosulfate with treating that degradation of contaminant is mixed, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method prepare catalytic membrane activation peroxy-monosulfate degradation of methylene blue (0.1mmol/L), Ah When Te Lajin (10 μm of ol/L), p-nitrophenol (0.1mmol/L) and sulfamethazine (10 μm of ol/L) solution, one is being crossed Sulfate dosage is 1mmol/L.Except rate has respectively reached 99.8%, 63.8%, 87.6% and 57.3%, and peroxy-monosulfate The clearance individually aoxidized is respectively 0.8%, 0.1%, 1.2% and 0.3%.It can be seen that catalytic membrane is catalyzed to peroxy-monosulfate Oxidation, which has, is obviously improved effect, and reaches higher removal efficiency within the extremely short time, is short time, high efficiency Remove organic pollutants and provide feasible method.
Embodiment 2：
First, flexible manganese dioxide film matrix is prepared
1) by 3.6g manganese sulfate, 3.2g potassium chlorate, and 3.7g potassium acetate are dissolved in 100mL deionized waters, stirring 30 minutes；
2) solution stirred is poured into 200mL hydrothermal reaction kettles, reacted 6 hours under conditions of 180 DEG C；
3) after reaction terminates, resulting sediment is filtered on 0.45 micron of glass fiber filter, in 65 DEG C of temperature Degree is lower to dry 12h, obtains manganese dioxide nanowire；
4) 0.1g manganese dioxide nanowires are taken, using ultrasonic disperse in the 100mL aqueous solution, using ultrasonic disperse certain In the aqueous solution of amount, filter on 0.45 micron of filter membrane, dried 30 minutes at a temperature of 65 DEG C, can be easily by softness Manganese dioxide nanowire membrane peeled above filter membrane, 0.45 micron of filter membrane is reusable；
5) in 500 DEG C of roasting temperature 2h, manganese dioxide nanowire membrane is obtained.
2nd, multi-level nano-structure catalytic membrane is prepared
1) take in the manganese dioxide film prepared, the mixed solution for being soaked in 5mmol/L copper acetates and ethanol, soak 15 seconds Take out afterwards after drying, repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.2g copper nitrates are dissolved in 100mL deionized waters, add 1.8mL ammoniacal liquor and stir；
3) the manganese dioxide film after will be calcined is put into the mixed solution of copper nitrate and ammoniacal liquor, is obtained after standing 6 hours The catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano piece.
Experiment effect：
By peroxy-monosulfate with treating that degradation of contaminant is mixed, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method prepare catalytic membrane activation peroxy-monosulfate degradation of methylene blue (0.1mmol/L), Ah When Te Lajin (10 μm of ol/L), p-nitrophenol (0.1mmol/L) and sulfamethazine (10 μm of ol/L) solution, one is being crossed Sulfate dosage is 1mmol/L.Except rate has respectively reached 99.1%, 53.8%, 67.6% and 87.3%.
Embodiment 3：
First, flexible manganese dioxide film matrix is prepared
1) 3.5g potassium permanganate is dissolved in 750mL deionized water, adds 150mL ethyl acetate at 85~95 DEG C Under the conditions of return stirring 2~3 days；
2) after reaction terminates, resulting sediment is filtered on 0.45 micron of glass fiber filter, in 65 DEG C of temperature Degree is lower to dry 12h, obtains manganese dioxide nanowire；
3) 1.5g manganese dioxide nanowires are taken, using ultrasonic disperse in the 1000mL aqueous solution, using ultrasonic disperse one In the quantitative aqueous solution, filter on 0.45 micron of filter membrane, dried 30 minutes at a temperature of 65 DEG C, can easily will be soft Soft manganese dioxide nanowire membrane is peeled above filter membrane, and 0.45 micron of filter membrane is reusable；
4) in 400 DEG C of roasting temperature 1h, manganese dioxide nanowire membrane is obtained.
2nd, multi-level nano-structure catalytic membrane is prepared
1) take in the manganese dioxide film prepared, the mixed solution for being soaked in 5mmol/L copper acetates and ethanol, soak 15 seconds Take out afterwards after drying, repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.2g copper nitrates are dissolved in 100mL deionized waters, add 0.5g hexamethylenetetramines and stir；
3) the manganese dioxide film after will be calcined is put into mixed solution, stand 30 minutes after 92 DEG C of hydro-thermal process 6~ 12 hours, obtain the catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano line.
Experiment effect：
By peroxy-monosulfate with treating that degradation of contaminant is mixed, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method prepare catalytic membrane activation peroxy-monosulfate degradation of methylene blue (0.1mmol/L), Ah When Te Lajin (10 μm of ol/L), p-nitrophenol (0.1mmol/L) and sulfamethazine (10 μm of ol/L) solution, one is being crossed Sulfate dosage is 1mmol/L.Except rate has respectively reached 98.1%, 78.2%, 57.8% and 59.3%.
Embodiment 4：
First, flexible manganese dioxide film matrix is prepared
1) 0.4g potassium permanganate and 1.2g ammonium chloride are dissolved in 100mL deionized waters, are stirred 1 hour；
2) solution stirred is poured into 200mL hydrothermal reaction kettles, reacted 12 hours under conditions of 180 DEG C；
3) after reaction terminates, resulting sediment is filtered on 0.45 micron of glass fiber filter, in 65 DEG C of temperature Degree is lower to dry 12h, obtains manganese dioxide nanowire；
4) 50mg manganese dioxide nanowires are taken, using ultrasonic disperse in the 100mL aqueous solution, the filter at 0.45 micron are filtered On film, dry 30 minutes, easily can take soft manganese dioxide nanowire membrane above filter membrane off at a temperature of 65 DEG C Come, 0.45 micron of filter membrane is reusable；
5) the high-temperature roasting 2h at a temperature of 450 DEG C, obtains manganese dioxide nanowire membrane.
2nd, multi-level nano-structure catalytic membrane is prepared
1) take in the manganese dioxide film prepared, the mixed solution for being soaked in 5mmol/L copper acetates and ethanol, soak 15 seconds Take out afterwards after drying, repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.75g copper nitrates are dissolved in 100mL deionized waters, add 0.45g hexamethylenetetramines and stir；
3) the manganese dioxide film after will be calcined is put into mixed solution, small in 87 DEG C of hydro-thermal process 12 after standing 30 minutes When, obtain the catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano line.
Experiment effect：
By peroxy-monosulfate with treating that degradation of contaminant is mixed, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method prepare catalytic membrane activation peroxy-monosulfate degradation of methylene blue (0.1mmol/L), Ah When Te Lajin (10 μm of ol/L), p-nitrophenol (0.1mmol/L) and sulfamethazine (10 μm of ol/L) solution, one is being crossed Sulfate dosage is 1mmol/L.Except rate has respectively reached 99.5%, 81.6%, 51.4% and 75.3%.

Claims (9)

1. the preparation method of multi-level nano-structure flexible inorganic film, it is characterised in that this method comprises the following steps：
First, flexible manganese dioxide film substrate is prepared：
The preparation method of the flexible manganese dioxide film substrate is method one, method two or method three；
Method one is：
Potassium permanganate and ammonium chloride are dissolved in deionized water, stirred 1~2 hour；
The solution stirred is poured into hydrothermal reaction kettle, reacted 12~36 hours under conditions of 160~220 DEG C；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, at a temperature of 65~70 DEG C 10~12h is dried, manganese dioxide nanowire is obtained；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~70 DEG C At a temperature of dry 30~40 minutes, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire membrane from Peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400~600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire membrane；
Method two is：
Potassium permanganate is dissolved in deionized water, ethyl acetate is added, return stirring 2~3 days under conditions of 85~95 DEG C；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, at a temperature of 65~70 DEG C 10~12h is dried, manganese dioxide nanowire is obtained；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~70 DEG C At a temperature of dry 30~40 minutes, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire membrane from Peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire membrane；
Method three is：
Manganese sulfate, potassium chlorate and potassium acetate are dissolved in deionized water, stirred 30~40 minutes；
The solution stirred is poured into hydrothermal reaction kettle, reacted 6~12 hours under conditions of 160~180 DEG C；
After reaction terminates, resulting sediment is filtered with 0.45 micron of glass fiber filter, at a temperature of 65~70 DEG C 10~12h is dried, manganese dioxide nanowire is obtained；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~70 DEG C At a temperature of dry 30~40 minutes, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire membrane from Peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, obtain manganese dioxide nanowire membrane；
2nd, multi-level nano-structure catalytic membrane is prepared：
The preparation method of the multi-level nano-structure catalytic membrane is method one or method two；
Method one：
The manganese dioxide nanowire membrane prepared is taken, in the mixed solution for being soaked in 0.05~0.1mol/L copper acetates and ethanol, Soak and drying is taken out after 10~15s, after repeating 3~5 times, be put into Muffle furnace and calcined 20~60 minutes at 200~400 DEG C；
Copper nitrate is dissolved in deionized water, ammoniacal liquor is added and stirs, obtain the mixed solution of copper nitrate and ammoniacal liquor；
Manganese dioxide nanowire membrane after will be calcined is put into the mixed solution of copper nitrate and ammoniacal liquor, after standing 12~48 hours Obtain the catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano piece；
Method two：
The manganese dioxide nanowire membrane prepared is taken, in the mixed solution for being soaked in 0.05~0.1mol/L copper acetates and ethanol, Soak and drying is taken out after 10~15s, after repeating 3~5 times, be put into Muffle furnace and calcined 20~60 minutes at 200~400 DEG C；
Copper nitrate is dissolved in deionized water, hexamethylenetetramine is added and stirs, obtain mixed solution；
Manganese dioxide nanowire membrane after will be calcined is put into mixed solution, 30~40 minutes is stood, then at 85~92 DEG C Hydro-thermal process 6~12 hours, obtains the catalytic membrane of the multi-level nano-structure of manganese oxide nano wire/cupric oxide nano line.
2. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step one The mass ratio of potassium permanganate, ammonium chloride and deionized water is (0.1~0.5) in method one：(0.4~3.4)：100.
3. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step one The mass ratio of potassium permanganate, ethyl acetate and deionized water is (1.2~3.5) in method two：(89~267)：750.
4. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step one Manganese sulfate in method three, potassium chlorate, the mass ratio of potassium acetate and deionized water are (1.2~3.6)：(0.8~3.2)：(0.63~ 3.7)：100.
5. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step 2 The mass ratio of copper nitrate, ammoniacal liquor and deionized water is (0.01~0.2) in method one：(0.9~2.7)：100.
6. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step 2 The mass ratio of copper nitrate, hexamethylenetetramine and deionized water is (0.01~0.2) in method two：(0.14~1.2)：100.
7. multi-level nano-structure flexible inorganic film prepared by the method described in claim 1 answering in catalysis peroxy-monosulfate With.
8. application according to claim 7, it is characterised in that cross a sulphur using multi-level nano-structure flexible inorganic Membrane catalysis The specific method of hydrochlorate is：By peroxy-monosulfate and treat degradation of contaminant mix, then using level nanostructured flexible inorganic film Mixture is filtered.
9. application according to claim 8, it is characterised in that it is described treat degradation of contaminant for methylene blue, Atrazine, P-nitrophenol or sulfamethazine.
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