CN107308948B - 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

Info

Publication number
CN107308948B
CN107308948B CN201710571526.9A CN201710571526A CN107308948B CN 107308948 B CN107308948 B CN 107308948B CN 201710571526 A CN201710571526 A CN 201710571526A CN 107308948 B CN107308948 B CN 107308948B
Authority
CN
China
Prior art keywords
manganese dioxide
membrane
dioxide nanowire
temperature
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710571526.9A
Other languages
Chinese (zh)
Other versions
CN107308948A (en
Inventor
梁恒
罗鑫圣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201710571526.9A priority Critical patent/CN107308948B/en
Publication of CN107308948A publication Critical patent/CN107308948A/en
Application granted granted Critical
Publication of CN107308948B publication Critical patent/CN107308948B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • 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
    • B01J20/28014—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • 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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Nanotechnology (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

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, need the problem of further recycling, be more troublesome.Method: one, flexible manganese dioxide film substrate is prepared；Two, 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 effectively improves catalytic oxidation efficiency, so that peroxy-monosulfate is highly efficient to the degradation of organic pollutant, thorough, inorganic catalytic membrane when being filtering due to being catalyzed, therefore without further recycling after use, and long service life, it can be used until breakage occurs for film itself.The present invention is used for sewage treatment field.

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 applications of flexible inorganic film.
Background technique
High-level oxidation technology is one kind by outside energy (luminous energy, thermal energy, ultrasonic wave good fortune are penetrated or microwave good fortune is penetrated) or urges The introducing of agent reaches activation H2O2Or O3The purpose of equal Green Oxidants, utilizes the active group generated in activation process such as hydroxyl Base free radical (OH) or potentiometric titrations (SO4-) degrade to organic pollutant and the oxidation technology of mineralising.Initially The high-level oxidation technology of proposition refers in particular to generally include Fenton oxidation technology, light is urged with the oxidation technology for active oxidation species 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 generated using persulfate activation4·-Degradable organic pollutant is becoming a kind of novel 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.In the underground water and soil of organic pollutant pollution In reparation, sodium peroxydisulfate (the 78g/100g H with highly-water-soluble is generallyd use2O,25℃).Peroxy-monosulfate mainly with 2KHSO5·KHSO4·K2SO4The form of three salt compounds exists, trade name Oxone.Wherein active material is single peroxide sulphur Sour oxygen potassium.Persulfuric acid salt form high-level oxidation technology is good with oxidant stability, dissolubility is good, and activation method is more, and pH is applicable in anti- The advantages that Ying Guang, strong anti-inorganic salts interference performance, and the SO generated4·-(half-life period in service life is 4s) (service life is less than 1 than OH μ s) it is long, be conducive to contact with pollutant, increase free radical to the chance of contaminant degradation.Therefore, with SO4·-Based on High-level oxidation technology, become the high-level oxidation technology of great development prospect.
The catalysis reaction of advanced oxidation reaction under current ambient temperature normal pressure general homogeneous catalysis and heterogeneous catalysis two respectively Major class.Homogeneous catalytic reaction is usually using metal ion as catalyst.But due to catalyst easy in inactivation in homogeneous catalytic reaction, Easily at salt slurry, separation is difficult, easily causes the disadvantages of secondary pollution, just gradually replaced by heterogeneous catalysis.
With the continuous development of nanotechnology, function nano material due to bigger serface and high catalytic activity and by It is widely used in catalytic field.However, nano-catalyst particles, which often reunite and form bulky grain material, leads to its catalytic activity It reduces, catalytic efficiency is not high, with methylene blue example, at least needs 0.5~1 hour using powder catalyst catalysis methylene blue The degradation rate of methylene blue can be made to reach 90% or more.
In addition, also needing further to recycle in powdered nanocatalyst operational process, more troublesome, service life It is shorter.
Summary of the invention
The present invention is to solve it is existing catalysis peroxy-monosulfate powdered nanocatalyst catalytic efficiency it is low, need into one Step recycling, the problem of being more troublesome, provides the preparation method and application of multi-level nano-structure flexible inorganic film.
The preparation method of multi-level nano-structure flexible inorganic film of the present invention, comprising the following steps:
One, flexible manganese dioxide film substrate is prepared:
The preparation method of the flexibility manganese dioxide film substrate is method one, method two or method three；
Method one are as follows:
Potassium permanganate and ammonium chloride are dissolved in deionized water, stirred 1~2 hour；
The solution stirred evenly is poured into hydrothermal reaction kettle, is reacted 12~36 hours under conditions of 160~220 DEG C；
After reaction, 0.45 micron of glass fiber filter of obtained sediment is filtered, in 65~70 DEG C of temperature The lower dry 10~12h of degree, obtains manganese dioxide nanowire；
According to required film thickness and diameter, manganese dioxide nanowire is taken, manganese dioxide nanowire ultrasonic disperse is existed It in distilled water, is filtered with 0.45 micron of glass fiber filter, 30~40 minutes dry at a temperature of 65~70 DEG C, the shape on filter membrane At manganese dioxide nanowire membrane, soft manganese dioxide nanowire membrane is peeled above filter membrane, 0.45 micron of glass fibers It is reusable to tie up 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.
Wherein the mass ratio of potassium permanganate, ammonium chloride and deionized water is (0.1~0.5): (0.4~3.4): 100
Method two are as follows:
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, 0.45 micron of glass fiber filter of obtained sediment is filtered, in 65~70 DEG C of temperature The lower dry 10~12h of degree, obtains manganese dioxide nanowire；
According to required film thickness and diameter, manganese dioxide nanowire is taken, manganese dioxide nanowire ultrasonic disperse is existed It in distilled water, is filtered with 0.45 micron of glass fiber filter, 30~40 minutes dry at a temperature of 65~70 DEG C, the shape on filter membrane At manganese dioxide nanowire membrane, soft manganese dioxide nanowire membrane is peeled above filter membrane, 0.45 micron of glass fibers It is reusable to tie up 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.
Wherein the mass ratio of potassium permanganate, ethyl acetate and deionized water is (1.2~3.5): (89~267): 750
Method three are as follows:
Manganese sulfate, potassium chlorate and potassium acetate are dissolved in deionized water, stirred 30~40 minutes；
The solution stirred evenly is poured into hydrothermal reaction kettle, is reacted 6~12 hours under conditions of 160~180 DEG C；
After reaction, 0.45 micron of glass fiber filter of obtained sediment is filtered, in 65~70 DEG C of temperature The lower dry 10~12h of degree, obtains manganese dioxide nanowire；
According to required film thickness and diameter, manganese dioxide nanowire is taken, manganese dioxide nanowire ultrasonic disperse is existed It in distilled water, is filtered with 0.45 micron of glass fiber filter, 30~40 minutes dry at a temperature of 65~70 DEG C, the shape on filter membrane At manganese dioxide nanowire membrane, soft manganese dioxide nanowire membrane is peeled above filter membrane, 0.45 micron of glass fibers It is reusable to tie up 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.
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.
Two, 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 acetate and ethyl alcohol is soaked in In, drying is taken out after impregnating 10~15s, 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, ammonium hydroxide is added and stirs evenly, obtains the mixed solution of copper nitrate and ammonium hydroxide；Its The mass ratio of middle copper nitrate, ammonium hydroxide 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 ammonium hydroxide, and it is small to stand 12~48 When after obtain the catalytic membrane of manganese oxide nano wire/cupric oxide nano piece multi-level nano-structure.
Method two:
The manganese dioxide nanowire membrane prepared is taken, the mixed solution of 0.05~0.1mol/L copper acetate and ethyl alcohol is soaked in In, drying is taken out after impregnating 10~15s, 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 evenly, obtains 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 hydro-thermal process 6~12 hours, obtain the catalytic membrane of manganese oxide nano wire/cupric oxide nano line multi-level nano-structure.
Application of the multi-level nano-structure flexible inorganic film of above method preparation in catalysis peroxy-monosulfate.
Method particularly includes: it is mixed by peroxy-monosulfate and to degradation of contaminant, then uses grade nanostructure flexible inorganic Film is filtered mixture.It is described to degradation of contaminant be methylene blue, Atrazine, p-nitrophenol or sulfanilamide (SN) dimethyl Pyrimidine, but it is not limited only to these pollutants.
The invention has the following advantages:
(1) the present invention provides a kind of flexible inorganic film with peroxy-monosulfate catalysis, flexible operation mode, behaviour It is simple to make method, raw material needed for preparing is easier to obtain.
(2) inorganic catalytic membrane prepared by the present invention with multi-level nano-structure, since for nanoscale structures, surface is thick Rough injustice, therefore the specific surface area of film is improved, by 19cm2/ g is increased to 44cm2/g.And then mass-transfer efficiency is increased, effectively Catalytic oxidation efficiency is improved, so that peroxy-monosulfate is highly efficient to the degradation of organic pollutant, thorough, is obtained Better effluent quality.For using methylene blue (MB) as model pollutant, activated using inorganic catalytic membrane of the invention One sulfate degradation of contaminant methylene blue, specifically mixes peroxy-monosulfate with pollutant, then uses nothing of the invention Machine catalytic membrane is filtered, and i.e. activation peroxy-monosulfate generates free radicals while filtering, to methylene blue (0.1mmol/L) Removal rate can reach 98.1%~99.8%.Catalytic process moment completes, and catalytic efficiency is efficient, according to first order kinetics (formula 1) it calculates, the observed rate constant that catalytic membrane activates PMS degradation MB is k '=24.6, is much higher than typical catalyst.
C in formula 10And ClConcentration respectively after the initial concentration of MB and filtering degradation.L is the thickness of film, and v is in film Fluid linear velocity, t ' are time of contact in film, and k ' is first order kinetics observed rate constant.
Peroxy-monosulfate activation 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 copper oxide are received Rice structure, can fully play manganese dioxide and oxidation copper compound urges the absorption of organic pollutant and the collaboration of peroxy-monosulfate Change degradation, makes the catalytic membrane of preparation that there are the multiple actions such as absorption, peroxy-monosulfate catalysis oxidation and film filtering, realize 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, generates free radicals so generally requiring activation, accelerates degradation rate.Manganese dioxide and copper oxide itself are without oxidation drop The efficiency of organic matter is solved, as catalyst, catalytic activation peroxy-monosulfate is generated free radicals.
(4) inorganic catalytic membrane of the invention when being filtering due to being catalyzed, without further recycling after use, and And long service life, it can be used until breakage occurs for film itself.Present invention is mainly applied to drinking water and chemical wastewater treatment.
Detailed description of the invention
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.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment Any combination.
Specific embodiment 1: the preparation method of present embodiment multi-level nano-structure flexible inorganic film, including following step It is rapid:
One, flexible manganese dioxide film substrate is prepared:
The preparation method of the flexibility manganese dioxide film substrate is method one, method two or method three；
Method one are as follows:
Potassium permanganate and ammonium chloride are dissolved in deionized water, stirred 1~2 hour；
The solution stirred evenly is poured into hydrothermal reaction kettle, is reacted 12~36 hours under conditions of 160~220 DEG C；
After reaction, 0.45 micron of glass fiber filter of obtained sediment is filtered, in 65~70 DEG C of temperature The lower dry 10~12h of degree, obtains manganese dioxide nanowire；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~ It is 30~40 minutes dry at a temperature of 70 DEG C, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire Film peels 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 are as follows:
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, 0.45 micron of glass fiber filter of obtained sediment is filtered, in 65~70 DEG C of temperature The lower dry 10~12h of degree, obtains manganese dioxide nanowire；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~ It is 30~40 minutes dry at a temperature of 70 DEG C, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire Film peels 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 are as follows:
Manganese sulfate, potassium chlorate and potassium acetate are dissolved in deionized water, stirred 30~40 minutes；
The solution stirred evenly is poured into hydrothermal reaction kettle, is reacted 6~12 hours under conditions of 160~180 DEG C；
After reaction, 0.45 micron of glass fiber filter of obtained sediment is filtered, in 65~70 DEG C of temperature The lower dry 10~12h of degree, obtains manganese dioxide nanowire；
By manganese dioxide nanowire ultrasonic disperse in distilled water, filtered with 0.45 micron of glass fiber filter, 65~ It is 30~40 minutes dry at a temperature of 70 DEG C, manganese dioxide nanowire membrane is formed on filter membrane, by soft manganese dioxide nanowire Film peels 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；
Two, 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 acetate and ethyl alcohol is soaked in In, drying is taken out after impregnating 10~15s, 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, ammonium hydroxide is added and stirs evenly, obtains the mixed solution of copper nitrate and ammonium hydroxide；
Manganese dioxide nanowire membrane after will be calcined is put into the mixed solution of copper nitrate and ammonium hydroxide, and it is small to stand 12~48 When after obtain the catalytic membrane of manganese oxide nano wire/cupric oxide nano piece multi-level nano-structure；
Method two:
The manganese dioxide nanowire membrane prepared is taken, the mixed solution of 0.05~0.1mol/L copper acetate and ethyl alcohol is soaked in In, drying is taken out after impregnating 10~15s, 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 evenly, obtains mixed solution；
Manganese dioxide nanowire membrane after will be calcined is put into mixed solution, stands 30~40 minutes, then 85~ 92 DEG C hydro-thermal process 6~12 hours, obtain the catalytic membrane of manganese oxide nano wire/cupric oxide nano line multi-level nano-structure.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: it is high in the method one of step 1 The mass ratio of potassium manganate, ammonium chloride and deionized water is (0.1~0.5): (0.4~3.4): 100.Other and specific embodiment One is identical.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: the method two of step 1 The mass ratio of middle potassium permanganate, ethyl acetate and deionized water is (1.2~3.5): (89~267): 750.Other and specific reality It is identical to apply mode one or two.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: the side of step 1 Manganese sulfate in method three, potassium chlorate, potassium acetate and deionized water mass ratio be (1.2~3.6): (0.8~3.2): (0.63~ 3.7): 100.It is other identical as one of specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: the side of step 2 The mass ratio of copper nitrate, ammonium hydroxide and deionized water is (0.01~0.2): (0.9~2.7): 100 in method one.Other and specific reality It is identical to apply one of mode one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: the side of step 2 The mass ratio of copper nitrate, hexamethylenetetramine and deionized water is (0.01~0.2): (0.14~1.2): 100 in method two.It is other It is identical as one of specific embodiment one to five.
Specific embodiment 7: present embodiment multi-level nano-structure flexible inorganic film answering in catalysis peroxy-monosulfate With.
Specific embodiment 8: present embodiment is unlike specific embodiment seven: soft using multi-level nano-structure Property inorganic Membrane catalysis peroxy-monosulfate method particularly includes: mixed by peroxy-monosulfate and to degradation of contaminant, then use grade Nanostructure flexible inorganic film is filtered mixture.It is other identical as specific embodiment seven.
Specific embodiment 9: present embodiment is unlike specific embodiment eight: described to be to degradation of contaminant Methylene blue, Atrazine, p-nitrophenol or sulfamethazine.It is other identical as specific embodiment eight.
Elaborate below to the embodiment of the present invention, following embodiment under the premise of the technical scheme of the present invention into 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:
One, flexible manganese dioxide film matrix is prepared
1) potassium permanganate of 0.1g and the ammonium chloride of 0.6g are dissolved in 100mL deionized water, are stirred 1 hour；
2) solution stirred evenly is poured into 200mL hydrothermal reaction kettle, is reacted 12 hours under conditions of 160 DEG C；
3) after reaction, by the filtering of obtained sediment on 0.45 micron of glass fiber filter, in 65 DEG C of temperature The lower dry 12h of degree, obtains manganese dioxide nanowire；
4) 50mg manganese dioxide nanowire is taken, using ultrasonic disperse in 100mL aqueous solution, filters the filter at 0.45 micron It is 30 minutes dry at a temperature of 65 DEG C on film, easily soft manganese dioxide nanowire membrane can be taken off above filter membrane Come, 0.45 micron of filter membrane is reusable；
5) high-temperature roasting 1h at a temperature of 450 DEG C, obtains manganese dioxide nanowire membrane.
Two, multi-level nano-structure catalytic membrane is prepared
1) the manganese dioxide film prepared is taken, is soaked in the mixed solution of 5mmol/L copper acetate and ethyl alcohol, is impregnated 15 seconds It takes out and dries afterwards, after repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.2g copper nitrate is dissolved in 100mL deionized water, 1.8mL ammonium hydroxide is added and stirs evenly；
3) the manganese dioxide film after will be calcined is put into the mixed solution of copper nitrate and ammonium hydroxide, is obtained after standing 6 hours The catalytic membrane of manganese oxide nano wire/cupric oxide nano piece multi-level nano-structure.
Experiment effect:
Peroxy-monosulfate is mixed with to degradation of contaminant, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method preparation 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 removal rate individually aoxidized is respectively 0.8%, 0.1%, 1.2% and 0.3%.It can be seen that catalytic membrane is catalyzed peroxy-monosulfate Oxidation, which has, is obviously improved effect, and reaches higher removal efficiency within the extremely short time, is short time, high efficiency Removal organic pollutants provide feasible method.
Embodiment 2:
One, flexible manganese dioxide film matrix is prepared
1) manganese sulfate of 3.6g, the potassium chlorate of 3.2g and the potassium acetate of 3.7g are dissolved in 100mL deionized water, are stirred 30 minutes；
2) solution stirred evenly is poured into 200mL hydrothermal reaction kettle, is reacted 6 hours under conditions of 180 DEG C；
3) after reaction, by the filtering of obtained sediment on 0.45 micron of glass fiber filter, in 65 DEG C of temperature The lower dry 12h of degree, obtains manganese dioxide nanowire；
4) 0.1g manganese dioxide nanowire is taken, using ultrasonic disperse in 100mL aqueous solution, using ultrasonic disperse certain In the aqueous solution of amount, filter on 0.45 micron of filter membrane, it, can easily will be soft dry 30 minutes at a temperature of 65 DEG C 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.
Two, multi-level nano-structure catalytic membrane is prepared
1) the manganese dioxide film prepared is taken, is soaked in the mixed solution of 5mmol/L copper acetate and ethyl alcohol, is impregnated 15 seconds It takes out and dries afterwards, after repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.2g copper nitrate is dissolved in 100mL deionized water, 1.8mL ammonium hydroxide is added and stirs evenly；
3) the manganese dioxide film after will be calcined is put into the mixed solution of copper nitrate and ammonium hydroxide, is obtained after standing 6 hours The catalytic membrane of manganese oxide nano wire/cupric oxide nano piece multi-level nano-structure.
Experiment effect:
Peroxy-monosulfate is mixed with to degradation of contaminant, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method preparation 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:
One, flexible manganese dioxide film matrix is prepared
1) potassium permanganate of 3.5g is dissolved in the deionized water of 750mL, and the ethyl acetate of 150mL is added at 85~95 DEG C Under the conditions of return stirring 2~3 days；
2) after reaction, by the filtering of obtained sediment on 0.45 micron of glass fiber filter, in 65 DEG C of temperature The lower dry 12h of degree, obtains manganese dioxide nanowire；
3) 1.5g manganese dioxide nanowire is taken, using ultrasonic disperse in 1000mL aqueous solution, using ultrasonic disperse one In quantitative aqueous solution, filter on 0.45 micron of filter membrane, it, can easily will be soft dry 30 minutes at a temperature of 65 DEG C Soft manganese dioxide nanowire membrane peels 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.
Two, multi-level nano-structure catalytic membrane is prepared
1) the manganese dioxide film prepared is taken, is soaked in the mixed solution of 5mmol/L copper acetate and ethyl alcohol, is impregnated 15 seconds It takes out and dries afterwards, after repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.2g copper nitrate is dissolved in 100mL deionized water, 0.5g hexamethylenetetramine is added and stirs evenly；
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 manganese oxide nano wire/cupric oxide nano line multi-level nano-structure.
Experiment effect:
Peroxy-monosulfate is mixed with to degradation of contaminant, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method preparation 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:
One, flexible manganese dioxide film matrix is prepared
1) potassium permanganate of 0.4g and the ammonium chloride of 1.2g are dissolved in 100mL deionized water, are stirred 1 hour；
2) solution stirred evenly is poured into 200mL hydrothermal reaction kettle, is reacted 12 hours under conditions of 180 DEG C；
3) after reaction, by the filtering of obtained sediment on 0.45 micron of glass fiber filter, in 65 DEG C of temperature The lower dry 12h of degree, obtains manganese dioxide nanowire；
4) 50mg manganese dioxide nanowire is taken, using ultrasonic disperse in 100mL aqueous solution, filters the filter at 0.45 micron It is 30 minutes dry at a temperature of 65 DEG C on film, easily soft manganese dioxide nanowire membrane can be taken off above filter membrane Come, 0.45 micron of filter membrane is reusable；
5) high-temperature roasting 2h at a temperature of 450 DEG C, obtains manganese dioxide nanowire membrane.
Two, multi-level nano-structure catalytic membrane is prepared
1) the manganese dioxide film prepared is taken, is soaked in the mixed solution of 5mmol/L copper acetate and ethyl alcohol, is impregnated 15 seconds It takes out and dries afterwards, after repeated several times, be put into Muffle furnace and calcined 35 minutes at 350 DEG C.
2) 0.75g copper nitrate is dissolved in 100mL deionized water, 0.45g hexamethylenetetramine is added and stirs evenly；
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 manganese oxide nano wire/cupric oxide nano line multi-level nano-structure.
Experiment effect:
Peroxy-monosulfate is mixed with to degradation of contaminant, mixture was carried out with catalytic membrane manufactured in the present embodiment Filter.
Using the present embodiment method preparation 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 method includes the following steps:
One, flexible manganese dioxide film substrate is prepared:
The preparation method of the flexibility manganese dioxide film substrate is method one, method two or method three；
Method one are as follows:
Potassium permanganate and ammonium chloride are dissolved in deionized water, stirred 1~2 hour；
The solution stirred evenly is poured into hydrothermal reaction kettle, is reacted 12~36 hours under conditions of 160~220 DEG C；
After reaction, 0.45 micron of glass fiber filter of obtained sediment is filtered, at a temperature of 65~70 DEG C 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, 65~70 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 It is peeled above filter membrane；
By manganese dioxide nanowire membrane, 1~2h of high-temperature roasting, the manganese dioxide after being roasted are received at a temperature of 400~600 DEG C Rice noodles film；
Method two are as follows:
Potassium permanganate is dissolved in deionized water, ethyl acetate is added, the return stirring 2~3 days under conditions of 85~95 DEG C；
After reaction, 0.45 micron of glass fiber filter of obtained sediment is filtered, at a temperature of 65~70 DEG C 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, 65~70 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 It is peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, the manganese dioxide nano after being roasted Line film；
Method three are as follows:
Manganese sulfate, potassium chlorate and potassium acetate are dissolved in deionized water, stirred 30~40 minutes；
The solution stirred evenly is poured into hydrothermal reaction kettle, is reacted 6~12 hours under conditions of 160~180 DEG C；
After reaction, 0.45 micron of glass fiber filter of obtained sediment is filtered, at a temperature of 65~70 DEG C 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, 65~70 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 It is peeled above filter membrane；
By manganese dioxide nanowire membrane at a temperature of 400-600 DEG C 1~2h of high-temperature roasting, the manganese dioxide nano after being roasted Line film；
Two, 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, is soaked in the mixed solution of 0.05~0.1mol/L copper acetate and ethyl alcohol, Drying is taken out after impregnating 10~15s, 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, ammonium hydroxide is added and stirs evenly, obtains the mixed solution of copper nitrate and ammonium hydroxide；
Manganese dioxide nanowire membrane after will be calcined is put into the mixed solution of copper nitrate and ammonium hydroxide, after standing 12~48 hours Obtain the catalytic membrane of manganese dioxide nanowire/cupric oxide nano piece multi-level nano-structure；
Method two:
The manganese dioxide nanowire membrane prepared is taken, is soaked in the mixed solution of 0.05~0.1mol/L copper acetate and ethyl alcohol, Drying is taken out after impregnating 10~15s, 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 evenly, obtains 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, obtain the catalytic membrane of manganese dioxide nanowire/cupric oxide nano line multi-level nano-structure.
2. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step 1 The mass ratio of potassium permanganate, ammonium chloride and deionized water is (0.1~0.5): (0.4~3.4): 100 in method one.
3. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step 1 The mass ratio of potassium permanganate, ethyl acetate and deionized water is (1.2~3.5): (89~267): 750 in method two.
4. the preparation method of multi-level nano-structure flexible inorganic film according to claim 1, it is characterised in that step 1 Manganese sulfate in method three, potassium chlorate, potassium acetate and deionized water mass ratio be (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, ammonium hydroxide and deionized water is (0.01~0.2): (0.9~2.7): 100 in method one.
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): (0.14~1.2): 100 in method two.
7. multi-level nano-structure flexible inorganic film the answering in catalysis peroxy-monosulfate of method preparation described in claim 1 With.
8. application according to claim 7, it is characterised in that cross a sulphur using multi-level nano-structure flexible inorganic Membrane catalysis Hydrochlorate method particularly includes: mixed by peroxy-monosulfate and to degradation of contaminant, then use multi-level nano-structure flexible inorganic Film is filtered mixture.
9. application according to claim 8, it is characterised in that it is described to degradation of contaminant be methylene blue, Atrazine, P-nitrophenol or sulfamethazine.
CN201710571526.9A 2017-07-13 2017-07-13 The preparation method and application of multi-level nano-structure flexible inorganic film Active CN107308948B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710571526.9A CN107308948B (en) 2017-07-13 2017-07-13 The preparation method and application of multi-level nano-structure flexible inorganic film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710571526.9A CN107308948B (en) 2017-07-13 2017-07-13 The preparation method and application of multi-level nano-structure flexible inorganic film

Publications (2)

Publication Number Publication Date
CN107308948A CN107308948A (en) 2017-11-03
CN107308948B true CN107308948B (en) 2019-09-13

Family

ID=60177923

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710571526.9A Active CN107308948B (en) 2017-07-13 2017-07-13 The preparation method and application of multi-level nano-structure flexible inorganic film

Country Status (1)

Country Link
CN (1) CN107308948B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109647324B (en) * 2019-01-03 2021-12-17 安庆师范大学 Adsorption film and preparation method and application thereof
CN115337935B (en) * 2022-07-26 2024-01-23 北方民族大学 Cu-MnO with high catalytic activity 2 Nano catalyst, preparation method and application thereof, and printing and dyeing wastewater treatment method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103058353A (en) * 2013-01-01 2013-04-24 东北电力大学 Method for removing pollutants in water by film process catalytic ozonation
CN103112899B (en) * 2013-03-05 2015-02-11 广东工业大学 Preparation method of functionalized manganese dioxide nanowire membrane
CN103495345B (en) * 2013-10-21 2015-09-09 哈尔滨工业大学 A kind of method of modifying for water treatment inorganic catalytic membrane
CN105597558B (en) * 2015-09-29 2018-11-13 浙江理工大学 A kind of composite nanometer filtering film with catalytic degradation function and preparation method thereof, application
CN105977501B (en) * 2016-05-19 2018-10-19 中南大学 A kind of high-performance hydrogen reduction MnO2-Mn3O4/ carbon nano tube composite catalyst and its preparation method and application

Also Published As

Publication number Publication date
CN107308948A (en) 2017-11-03

Similar Documents

Publication Publication Date Title
CN109574317B (en) Method for degrading fluoroquinolone antibiotics by activating peracetic acid through lanthanoid ruthenate perovskite
CN102078807B (en) Er<3+>:YAlO3/TiO2-loaded photocatalyst and preparation method thereof
Gholami et al. Sonophotocatalytic degradation of sulfadiazine by integration of microfibrillated carboxymethyl cellulose with Zn-Cu-Mg mixed metal hydroxide/g-C3N4 composite
CN109248680B (en) Low-energy-consumption chemical field-driven organic pollutant degradation catalyst and application thereof
CN111001413B (en) Catalyst for oxidizing and degrading ibuprofen by sulfate radical and preparation method thereof
CN112958089B (en) Preparation method of copper oxide catalyst for catalyzing persulfate to degrade pollutants in water
CN105363433B (en) Graphene-based bismuth tungstate composite photocatalyst and its preparation method and application
CN107008467A (en) The preparation method and purposes of a kind of heterojunction photocatalyst
CN107175112A (en) A kind of micro motor photochemical catalyst and its preparation method and application
CN104909427A (en) Construction and application method of photoassisted porous copper bismuthate activated persulfate water treatment high-grade oxidation technology
CN107308948B (en) The preparation method and application of multi-level nano-structure flexible inorganic film
CN109225186A (en) Titanium dioxide and silicon dioxide composite material catalyst, preparation and application
CN106630102B (en) Application and method for degrading organic wastewater by using Ce-OMS-2 catalyst
CN112142097A (en) Cadmium stannate trihydrate, and preparation method and application thereof
CN108722445A (en) A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application
CN103846099B (en) A kind of support type polyoxometallate and preparation method thereof
Du et al. Insights into the photocatalytic activation of peroxymonosulfate by visible light over BiOBr-cyclodextrin polymer complexes for efficient degradation of dye pollutants in water
CN111617759B (en) Manganese dioxide nano catalytic film for catalyzing ozone to degrade organic wastewater and preparation method thereof
CN106673171A (en) Method for promoting peroxymonosulfate to generate sulfate radicals for degrading organic matters
CN109574193B (en) Ruthenium ruthenate lanthanide perovskite catalyst and method for degrading carbamazepine by heterogeneous activated peroxymonosulfate
CN108940349A (en) The method of carbonitride Z-type photochemical catalyst removal dyestuff contaminant is mixed using siliver chromate/sulphur
CN109092360A (en) A kind of preparation method of the nano hybridization gel mould for catalytic degradation organic matter
CN111013588B (en) Fenton-like catalyst and preparation method and application thereof
CN111437850A (en) Composite visible light catalyst and preparation method and application thereof
CN104150524A (en) Preparation method of zinc oxide visible-light-induced photocatalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant