CN109137009A - A kind of method that pulse electrodeposition prepares porous magnesium hydroxide - Google Patents
A kind of method that pulse electrodeposition prepares porous magnesium hydroxide Download PDFInfo
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- CN109137009A CN109137009A CN201811156287.1A CN201811156287A CN109137009A CN 109137009 A CN109137009 A CN 109137009A CN 201811156287 A CN201811156287 A CN 201811156287A CN 109137009 A CN109137009 A CN 109137009A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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Abstract
A kind of method that pulse electrodeposition prepares porous magnesium hydroxide, belongs to the technical field of sewage treatment adsorbent material.Porous magnesium hydroxide is prepared with the method for pulse electrodeposition on titania nanotube.Pulse electrodeposition provided by the invention prepares the technology of porous magnesium hydroxide, can increase substantially chromium ion adsorption rate, and safety and stability is easily recycled, to solve the problems, such as that the recycling of Conventional nano magnesium hydroxide difficulty provides a new effective measures with easy to reunite.
Description
Technical field
The present invention relates to a kind of methods that pulse electrodeposition prepares porous magnesium hydroxide, belong to sewage treatment adsorbent material
Technical field.
Background technique
Increasingly developed with science and technology, performance is more and environmentally protective functionalization material becomes people's research and development and raw
One of main purpose of production.Magnesium hydroxide is a kind of large specific surface area, the strong alkalescent environment-friendly type adsorbent of active site, due to
Stronger solution buffering effect and particle absorption ability it is strong and using it is safe the features such as, have it in environment protection field very huge
Development potentiality.Traditional magnesium hydroxide specific surface is small, and limited sorption capacity, nanoscale magnesium hydroxide specific surface is big, absorption
Performance is good, but is easy to reunite, while traditional magnesium hydroxide is mostly powder, it is difficult to recycle.It is asked greatly based on hardly possible recycling and amount easy to reunite
Topic, the present invention propose to deposit nanoporous magnesium hydroxide membranoid substance on titania nanotube with the technology of pulse electrodeposition
Matter.Its porous pattern has great surface area, can quick adsorption test solution in Cd2+, while membranaceous magnesium hydroxide is easy
In recycling and secondary use, secondary pollution is avoided, there is very strong realistic meaning.Wherein electrodeposition method operation letter
Just, at low cost, high-efficient.
Summary of the invention
A kind of method that pulse electrodeposition prepares porous magnesium hydroxide of the present invention, using anodizing technology on Titanium
The Nano tube array of titanium dioxide for preparing high-sequential is deposited on Nano tube array of titanium dioxide using electrodeposition method
Porous magnesium hydroxide.Prepared sample carries out Cd2+Absorption property is tested, wherein the Cd of 40ppm2+Test solution adsorbance most
Big by reachable 99.5%, the test solution adsorbance that the sample adsorbance of three kinds of sedimentation times reaches 99% or more, 70ppm is maximum
It can reach 90%, the adsorbance of the sample of three kinds of sedimentation times reaches 83% or more.Pulse electrodeposition system provided by the invention
The technology of standby porous magnesium hydroxide can increase substantially the specific surface area of magnesium hydroxide, improve Cd2+Ionic adsorption rate, and
Safety and stability is easily recycled, and avoids secondary pollution, provides one to solve traditional magnesium hydroxide difficulty recycling with easy to reunite
New effective measures.
Preparation method provided by the invention, comprising the following steps:
(1) metal titanium sheet pre-processes: the oxide layer generated during metal titanium sheet surface and oil contaminant and storage is super by physics
Sound and chemical pickling process remove；It is preferred that specifically being cleaned using dish washing liquid, ethyl alcohol, deionized water ultrasound take out pickling after drying,
Pickling solution is preferably HF (analysis is pure), HNO3(analysis is pure), H2The mixed solution of O (preferably 1:3:6 volume ratio), is going after pickling
Ultrasound 10min, is dried for standby in ionized water；
(2) anodic oxidation: step (1) pretreated metal titanium sheet is in the inorganic solution Anodic Oxidation containing fluorine ion.
Sample is taken out after oxidation, is rinsed with deionized water, is dried, it is spare；The inorganic solution that preferred anodes oxidation uses is every
3gNH4HF2、57.515gNH4H2PO3 corresponds to 1LH2The mixed solution that O is formed；
(3) it is heat-treated: the sample that step (2) obtains 450 DEG C of heat treatment, 2 DEG C of min of heating rate in tube furnace-1, heat preservation
2h cools to room temperature with the furnace.
(4) pulse electrodeposition: the sample cut growth after heat treatment is rectangular, with rosin paraffin copper conductor and wherein one side
It is sealed, sample is placed in prepared electrolyte, the ingredient of electrolyte is magnesium nitrate and sodium acetate；Sample is positive electricity
Pole, metal platinized platinum are negative electrode, and voltage is arranged to 10ma, -15ma, burst length 2ms, sedimentation time 1-10min；Observe sample
There is significant change in product surface, and macroscopic white membranaceous material occur in sample surfaces as time went on.
The concentration of magnesium nitrate is 0.05-2mol/L in electrolyte, the concentration of sodium acetate is 0.05-2mol/L, preferably nitric acid
The concentration of magnesium is 0.1mol/L, the concentration of sodium acetate is 0.1mol/L.
Performance test: magnesium hydroxide produced by the present invention is that the connection of curved lamellar magnesium hydroxide forms fluffy three-dimensional
Perforated membrane further forms nano-porous film shape, for the heavy metal ion Cd in absorption effluent2+；Use chromium sulfate for chromium
The test solution of 40ppm and two kinds of concentration of 70ppm are prepared in source, sample prepared by step (4) pulse electrodeposition are completely immersed in molten
In liquid, the magnetic agitation of appropriate revolving speed is carried out, adsorbs 0-4h, the solution after taking absorption carries out ICP measurement Cd2+Concentration.
Compared with prior art, the beneficial effects of the present invention are:
The Nano tube array of titanium dioxide for preparing high-sequential in metal titanium sheet using anodizing technology, using pulse
The method of electro-deposition deposits cellular magnesium hydroxide membrane structure on titania nanotube.Prepared sample is inhaled
Attached performance test, under appropriate stirring, when adsorbing 1h, the Cd2+ test solution adsorbance maximum of 40ppm can reach 99.5%, three
The test solution adsorbance maximum that the adsorbance of the sample of kind sedimentation time reaches 99% or more, 70ppm can reach 90%, three
The adsorbance of the sample of kind sedimentation time reaches 83% or more.The substrate of immobilized cellular magnesium hydroxide is one in step (4)
The loose Nano tube array of titanium dioxide of kind, the hydrogen that the titania nanotube and pulse electrodeposition of anodizing preparation generate
Magnesia combines, and changes the pattern of magnesium hydroxide, successfully prepares cellular magnesium hydroxide.The magnesium hydroxide that the present invention obtains
For the cellular membrane structure of lamellar composition, technical solution is reproducible, excellent effect, obvious.
Detailed description of the invention
There are four attached drawings by the present invention, are now respectively described below:
The SEM of Fig. 1: pulse electrodeposition 1min porous magnesium hydroxide schemes；
The SEM of Fig. 2: pulse electrodeposition 3min porous magnesium hydroxide schemes；
The SEM of Fig. 3: pulse electrodeposition 5min porous magnesium hydroxide schemes；
Fig. 4: XRD diffracting spectrum after pulse electrodeposition.
Specific embodiment
Pulse electrodeposition of the present invention illustrated below prepares the specific embodiment of the method for porous magnesium hydroxide, but this
Invention is not limited to following embodiment.
Pretreated metal titanium sheet is received using the titanium dioxide that anodizing prepares high-sequential in following embodiment
Mitron: anodic oxidation (inorganic solution 3gNH is carried out in the inorganic solution containing fluorine ion4HF2、57.515gNH4H2PO3、
1LH2The mixed solution of O), oxidation voltage 20V aoxidizes 30min, oxidation voltage 10V, aoxidizes 10min, oxidation voltage 20V, then oxygen
Change 30min, oxidation voltage 10V, reoxidize 10min, last oxidation voltage 20V, aoxidizes 4h, sample is taken out, deionized water is used
It rinses, is dried for standby.The concentration of magnesium nitrate is 0.1mol/L in electrolyte, the concentration of sodium acetate is 0.1mol/L.
Embodiment 1
By metal titanium sheet ultrasound 10min, pickling processes, in the inorganic solution system Anodic Oxidation 4h containing fluorine ion,
Ultrasound drying, is cut into 1 × 1 ㎝ for the sample after heat treatment after 450 DEG C of heat treatment2Square, with rosin paraffin copper
Conducting wire be wherein sealed on one side, sample is placed in prepared electrolyte, the ingredient of electrolyte is magnesium nitrate and vinegar
Sour sodium.Sample is positive electrode, and metal platinized platinum is negative electrode, and voltage is arranged to 10ma, -15ma, time 2ms, sedimentation time
1min,
Embodiment 2
By metal titanium sheet ultrasound 10min, pickling processes, in the inorganic solution system Anodic Oxidation 4h containing fluorine ion,
Ultrasound drying, is cut into 1 × 1 ㎝ for the sample after heat treatment after 450 DEG C of heat treatment2Square, with rosin paraffin copper
Conducting wire be wherein sealed on one side, sample is placed in prepared electrolyte, the ingredient of electrolyte is magnesium nitrate and vinegar
Sour sodium.Sample is positive electrode, and metal platinized platinum is negative electrode, and voltage is arranged to 10ma, -15ma, time 2ms, sedimentation time
3min,
Embodiment 3
By metal titanium sheet ultrasound 10min, pickling processes, in the inorganic solution system Anodic Oxidation 4h containing fluorine ion,
Ultrasound drying, is cut into 1 × 1 ㎝ for the sample after heat treatment after 450 DEG C of heat treatment2Square, with rosin paraffin copper
Conducting wire be wherein sealed on one side, sample is placed in prepared electrolyte, the ingredient of electrolyte is magnesium nitrate and vinegar
Sour sodium.Sample is positive electrode, and metal platinized platinum is negative electrode, and voltage is arranged to 10ma, -15ma, time 2ms, sedimentation time
5min,
Above-described embodiment is reproducible, and embodiment 1-3 obtains essentially identical technical effect, porous after pulse electrodeposition
Magnesium hydroxide SEM figure is shown in Fig. 1, Fig. 2, Fig. 3, and the XRD diffraction pattern of the magnesium hydroxide after pulse electrodeposition is shown in that Fig. 4, absorption property are surveyed
Test result is shown in list 1 and list 2.
1 embodiment 2 of table adsorbs Cd2+ (40ppm) performance test summary sheet
2 embodiment 2 of table adsorbs Cd2+ (70ppm) performance test summary sheet
Claims (6)
1. a kind of method that pulse electrodeposition prepares porous magnesium hydroxide, which comprises the following steps:
(1) metal titanium sheet pre-process: metal titanium sheet surface and oil contaminant and storage during generate oxide layer by physics ultrasound with
The removal of chemical pickling process；
(2) anodic oxidation: step (1) pretreated metal titanium sheet is in the inorganic solution Anodic Oxidation containing fluorine ion.Oxidation
After take out sample, rinsed with deionized water, dry, it is spare；The inorganic solution that preferred anodes oxidation uses is every
3gNH4HF2、57.515gNH4H2PO3 corresponds to 1LH2The mixed solution that O is formed；
(3) it is heat-treated: the sample that step (2) obtains 450 DEG C of heat treatment, 2 DEG C of min of heating rate in tube furnace-1, 2h is kept the temperature,
Cool to room temperature with the furnace.
(4) pulse electrodeposition: the sample cut growth after heat treatment is rectangular, and copper conductor and wherein one side are sealed with rosin paraffin
Together, sample is placed in prepared electrolyte, the ingredient of electrolyte is magnesium nitrate and sodium acetate；Sample is positive electrode,
Metal platinized platinum is negative electrode, and voltage is arranged to 10ma, -15ma, burst length 2ms, sedimentation time 1-10min；Observe sample
There is significant change in product surface, and macroscopic white membranaceous material occur in sample surfaces as time went on.
2. the method that a kind of pulse electrodeposition described in accordance with the claim 1 prepares porous magnesium hydroxide, which is characterized in that step
(1) it is specifically cleaned using dish washing liquid, ethyl alcohol, deionized water ultrasound, takes out pickling after drying, pickling solution is preferably HF (analysis
It is pure), HNO3(analysis is pure), H2The mixed solution of O volume ratio 1:3:6, ultrasound 10min, drying are standby in deionized water after pickling
With.
3. the method that a kind of pulse electrodeposition described in accordance with the claim 1 prepares porous magnesium hydroxide, which is characterized in that electrolysis
The concentration of magnesium nitrate is 0.05-2mol/L in liquid, the concentration of sodium acetate is 0.05-2mol/L.
4. the method that a kind of pulse electrodeposition described in accordance with the claim 1 prepares porous magnesium hydroxide, which is characterized in that electrolysis
The concentration of magnesium nitrate is 0.1mol/L in liquid, the concentration of sodium acetate is 0.1mol/L.
5. being curved lamellar hydrogen according to the porous magnesium hydroxide that the described in any item methods of claim 1-4 are prepared
Magnesia connection forms fluffy three-dimensional porous membrane.
6. according to the application for the porous magnesium hydroxide that the described in any item methods of claim 1-4 are prepared, for adsorbing dirt
Heavy metal ion Cd in water2+。
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| CN201811156287.1A CN109137009B (en) | 2018-09-28 | 2018-09-28 | Method for preparing porous magnesium hydroxide by pulse electrodeposition |
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| CN201811156287.1A CN109137009B (en) | 2018-09-28 | 2018-09-28 | Method for preparing porous magnesium hydroxide by pulse electrodeposition |
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| CN109137009B CN109137009B (en) | 2021-02-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113463156A (en) * | 2021-07-23 | 2021-10-01 | 中国科学院青海盐湖研究所 | Magnesium hydroxide film layer and preparation method and system thereof |
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| CN1958851A (en) * | 2006-09-29 | 2007-05-09 | 浙江大学 | Method for preparing anthoid crystalline magnesium hydroxide film in microcosmic appearance |
| CN102834551A (en) * | 2011-03-08 | 2012-12-19 | 纳米及先进材料研发院有限公司 | Method for producing white anodized aluminum oxide |
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2018
- 2018-09-28 CN CN201811156287.1A patent/CN109137009B/en active Active
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| US4246075A (en) * | 1979-03-19 | 1981-01-20 | Marine Resources Company | Mineral accretion of large surface structures, building components and elements |
| CN1958851A (en) * | 2006-09-29 | 2007-05-09 | 浙江大学 | Method for preparing anthoid crystalline magnesium hydroxide film in microcosmic appearance |
| CN102834551A (en) * | 2011-03-08 | 2012-12-19 | 纳米及先进材料研发院有限公司 | Method for producing white anodized aluminum oxide |
| CN104789957A (en) * | 2015-03-12 | 2015-07-22 | 天津大学 | Microwave preparation method of flower-shaped hydroxyapatite coating layer on surface of magnesium alloy |
| CN106086990A (en) * | 2016-08-04 | 2016-11-09 | 北京工业大学 | A kind of method of the immobilized molybdenum bisuphide of porous titania thin films |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113463156A (en) * | 2021-07-23 | 2021-10-01 | 中国科学院青海盐湖研究所 | Magnesium hydroxide film layer and preparation method and system thereof |
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