CN100547119C - A kind ofly contain the preparation method that microscopic appearance is flower-shaped crystalline magnesium hydroxide film - Google Patents
A kind ofly contain the preparation method that microscopic appearance is flower-shaped crystalline magnesium hydroxide film Download PDFInfo
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- CN100547119C CN100547119C CNB2006100536885A CN200610053688A CN100547119C CN 100547119 C CN100547119 C CN 100547119C CN B2006100536885 A CNB2006100536885 A CN B2006100536885A CN 200610053688 A CN200610053688 A CN 200610053688A CN 100547119 C CN100547119 C CN 100547119C
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Abstract
The invention discloses a kind of preparation method that microscopic appearance is flower-shaped crystalline magnesium hydroxide film that contains.It is to use ionic liquid as additive, is the aqueous solution of magnesium nitrate and sodium-acetate by electrolytic solution, adopts the cathode electrodeposition method to prepare the magnesium hydroxide film that microscopic appearance is a nano flower-like.The concentration of magnesium nitrate is at 0.1～0.2mol/L in the electrolytic solution, and the concentration of sodium-acetate is at 0.025～0.2mol/L.By changing the concentration of sodium-acetate in the electrolytic solution, microscopic appearance is that the ratio of flower-shaped crystalline magnesium hydroxide in film is 5%～100%.That preparation method of the present invention has is easy to operate, save energy, the advantage that can at room temperature carry out.
Description
Technical field
The present invention relates to the preparation method of nano thin-film, especially contain the preparation method that microscopic appearance is flower-shaped crystalline magnesium hydroxide film.
Background technology
Magnesium hydroxide is the tabular crystal of hexagonal system, is a kind of inorganic weak bases series products, is insoluble in water, can be dissolved in strongly acidic solution.Magnesium hydroxide has the performance of higher activity and adsorptive power, safe in utilization, non-corrosiveness, many excellences such as nontoxic, has widely as " eco-friendly fire retardant ", " neutralizing agent of green safety gentleness " and sorbent material etc. and uses.
Magnesium hydroxide is a kind of novel inorganic combustion inhibitor of developing in recent years, has Heat stability is good, pollution-free, advantage such as smoke suppressing effect is good.Similar inorganic combustion inhibitor with other is compared, and it has better smoke suppressing effect.Since use and discarded process in all unharmful substance dischargings, and can also in and the acidity and the corrosive gases that produce in the combustion processes, also be a kind of environment-friendly fire retardant therefore, be the environmentally friendly inorganic combustion inhibitor that has better development prospect at present.
Magnesium hydroxide has unique buffering and neutralising capacity as alkali, and corrodibility is low, and in use the pH value is the highest can not surpass 9, N-process is mild, and precipitation crystal grain is bigger, and settling velocity is fast, mud is easy to filter and discharging, has reduced mud sediment volume, has reduced processing cost.These advantages make magnesium hydroxide be used widely in papermaking, printing and dyeing, leather, plating, city domestic sewage and fluorine-containing etc. acid waste water are handled.Magnesium hydroxide also is applicable to and contains sour waste gas (as SO simultaneously
2, HCl, NOx) processing.Therefore, magnesium hydroxide is a kind of " neutralizing agent of green safety gentleness ".
Magnesium hydroxide has high adsorption capacity and active big, can adsorb and remove environmentally harmful Ni from industrial effluent
2+, Cd
2+, Mn
2+, Cr
3+, Cr
6+Etc. heavy metal ion.The solubility product of magnesium hydroxide is bigger than common metal oxyhydroxide, handles heavy metal ion except adsorption takes place with magnesium hydroxide, also can remove deleterious heavy metal ion because of metathesis, has improved treatment effect.Magnesium hydroxide takes off fields such as ammonium and decolorization of dyeing and also has widespread use at flue gas desulfurization, removing phosphate in addition.
Calcium hydroxide method is a kind of traditional method for preparing magnesium hydroxide, with Ca (OH)
2Be precipitation agent, reaction formula is: Mg
2++ Ca (OH)
2=Mg (OH)
2↓+Ca
2+The advantage of this method is that raw material is easy to get, and production technique is simple.But because product granularity little (can reach 0.5 μ m following), poly-attached tendency is big, is difficult to sedimentation, filtration and washing, and easily adsorbs impurity, and product purity is lower, be mainly used in in not high flue gas desulfurization of magnesium hydroxide purity requirement and the acid waste water and etc.
Ammonia process also is a kind of important method of producing magnesium hydroxide, is precipitation agent with ammoniacal liquor, and reaction formula is: Mg
2++ 2NH
3H
2O=Mg (OH)
2↓+2NH
4 +Can make the fine magnesium hydroxide products of high purity, be applicable to the industries high such as medicine, chemical reagent and electronic-grade magnesium hydroxide purity requirement.But because the utilization ratio of ammoniacal liquor is low, the production cost height, and because the volatilization of ammoniacal liquor easily causes environmental pollution.
Sodium hydroxide method is to be precipitation agent with sodium hydroxide, and reaction formula is: Mg
2++ 2NaOH=Mg (OH)
2↓+2Na
+Adding speed by control sodium hydroxide in the production process can obtain the product that different grain size distributes, and purity is higher.But because sodium hydroxide is highly basic, can generate colloidal precipitation if condition control is improper, particle diameter is less than normal, brings difficulty not only for the control and the filtration of product performance, and easily brings more Na into
+And Cl
-, so this method requires comparatively strict to working condition.The raw materials cost height of this technology, the investment of by product treatment facility is big.
The barium hydrosulfide method is that equation is as follows: MgCl with barium hydrosulfide and magnesium chloride
2+ Ba (SH)
2+ 2H
2O=Mg (OH)
2↓+BaCl
2+ H
2S ↑.Magnesium hydroxide products purity height, the epigranular of this method preparation can be used for the higher high purity magnesium hydroxide product of the quality of production.But its main drawback is that the magnesium hydroxide particle that forms is little, filtration washing is difficult, and H
2S and BaCl
2All poisonous, can cause environmental pollution.
Above-mentioned several method for preparing magnesium hydroxide all is more traditional industrial process, and these methods respectively have its merits and demerits.It is size and the microscopic appearance that is difficult to the prepared magnesium hydroxide crystal of effectively control that but also there is a general shortcoming in these methods.
The size of inorganic nano-particle and microscopic appearance have significant effects to its physicochemical property, can carry out cutting to its physicochemical property by adjusting inorganic nano-particle size and microscopic appearance.Recently, document [1] has reported that liquid-phase precipitation method has synthesized the magnesium hydroxide nanocrystal with needle-like, stratiform and bar-shaped different-shape by adopting different complexing dispersion agents.Document [2] has reported that further with the synthetic microscopic appearance of hydrothermal technique be flower-shaped crystalline magnesium hydroxide, but hydro-thermal reaction needs higher temperature of reaction (95-135 ℃) and long reaction times (18 hours).Therefore, this method need consume the more energy.Kamath etc. [3] have just proposed to prepare with electrochemistry cathodic reduction deposition the method for metal hydroxides film as far back as 1998.The method of this liquid electrodeposition can prepare larger area metal hydroxides film easily, has advantages such as service temperature is low, the reaction times short, can use that different substrates and film thickness can accurately be controlled.Recently, Kamath etc. [4] have prepared magnesium hydroxide film with the method for this electrochemistry cathodic deposition, and magnesium hydroxide crystal is irregular small thin slices pattern.And so far, containing microscopic appearance with the direct preparation of electrochemistry cathodic deposition method is that flower-shaped crystalline magnesium hydroxide film yet there are no report.
[1]Jianping?Lv，Longzhen?Qiu，Baojun?Qu，Controlled?growth?of?threemorphological?structures?of?magnesium?hydroxide?nanoparticles?by?wetprecipitation?method，J.Crystal?Growth，2004，267：676-684.
[2]Chenglin?Yana，Dongfeng?Xuea，_，Longjiang?Zoub，Xiaoxing?Yana，Wen?Wanga，Preparation?of?magnesium?hydroxide?nanoflowers?Journal?of?Crystal?Growth，2005，282：448-454.
[3]G.H.A.Therese，P.V.Kmamth，Cathodic?reduction?of?di.erent?metal?saltsolutions?Part?I：synthesis?of?metal?hydroxides?by?electrogeneration?of?base，J.Applied?Electrochemistry，1998，28：539-543.
[4]M.Dinamani，P.V.Kamath，Electrosynthesis?of?Mg(OH)
2?coatings?on?stainlesssteel?substrates，J.of?Applied?Electrochemistry，2004，34：899-902.
Summary of the invention
The present invention relates to a kind of preparation method that microscopic appearance is flower-shaped crystalline magnesium hydroxide film that contains.
It is that the aqueous solution with magnesium nitrate and sodium-acetate is electrolytic solution, adopts the cathode electrodeposition method to prepare the magnesium hydroxide film that microscopic appearance is a nano flower-like.
The concentration of magnesium nitrate is at 0.1～0.2mol/L in the described electrolytic solution, and the concentration of sodium-acetate is at 0.025～0.2mol/L.The negative electrode that adopts is ITO (indium doped stannum oxide) conductive glass or a stainless steel.
Have following outstanding advantage with prior art comparison the present invention:
1) be that flower-shaped crystalline magnesium hydroxide compares with the synthetic microscopic appearance of existing hydrothermal method, of the present inventionly in liquid phase, prepare microscopic appearance to be that flower-shaped crystalline magnesium hydroxide method has temperature low (at room temperature just can realize), time short, therefore save energy greatly with electrochemistry cathode electrodeposition method.
2) can directly to prepare microscopic appearance be flower-shaped crystalline magnesium hydroxide film to the inventive method, what that flow through electric weight on the control electrode can control the thickness of film easily by.
3) the inventive method is by changing the content of sodium-acetate in the solution, and can adjust microscopic appearance effectively is the ratio of flower-shaped crystalline magnesium hydroxide in whole film.
Description of drawings
Fig. 1 is the XRD figure of the magnesium hydroxide film of cathode electrodeposition method preparation, and among the figure: (a) electrolytic solution is the aqueous solution of 0.1mol/L magnesium nitrate and 0.2mol/L sodium-acetate; (b) electrolytic solution is the 0.1mol/L magnesium nitrate aqueous solution;
Fig. 2 (a) is that electrolytic solution is the SEM photo of magnesium hydroxide film of cathode electrodeposition method preparation of the aqueous solution of 0.1mol/L magnesium nitrate and 0.2mol/L sodium-acetate;
Fig. 2 (b) is that electrolytic solution is the SEM photo of magnesium hydroxide film of cathode electrodeposition method preparation of the aqueous solution of 0.1mol/L magnesium nitrate aqueous solution;
The SEM photo of the magnesium hydroxide film of Fig. 3 cathode electrodeposition method preparation, electrolytic solution is the aqueous solution of 0.1mol/L magnesium nitrate and 0.025mol/L sodium-acetate;
The SEM photo of the magnesium hydroxide film of Fig. 4 cathode electrodeposition method preparation, electrolytic solution is the aqueous solution of 0.1mol/L magnesium nitrate and 0.1mol/L sodium-acetate;
The SEM photo of the magnesium hydroxide film of Fig. 5 cathode electrodeposition method preparation, electrolytic solution is the aqueous solution of 0.2mol/L magnesium nitrate and 0.15mol/L sodium-acetate.
Embodiment
Reaction process of the present invention can be expressed as:
NO
3 -+H
2O+2e
-＝NO
2 -(or?NH
3，N
2)+2OH
- (1)
2H
2O+2e
-＝2OH
-+H
2 (2)
Mg
2++nOH
-＝Mg(OH)
2 (3)
Jumping out when electrolysis contains the solution of magnesium nitrate in website oneself, at negative electrode the electrode reaction of (1) and (2) takes place, and according to reaction (1) and (2), produces the OH-ion near cathode surface.Because Mg (OH)
2Solubleness very little, its solubility product K
Sp=5.6 * 10
-12, the pH value that is to say at solution reaches 9 when above, Mg (OH)
2Can precipitation separate out.Therefore, in electrolytic process, according to reaction (1) and (2), near the pH value the cathode surface can raise, and makes Mg (OH)
2Precipitation is separated out at cathode surface.
When adding a certain amount of sodium-acetate in the electrolytic solution, sodium-acetate can change the microscopic appearance of the magnesium hydroxide of cathodic deposition preparation, makes magnesium hydroxide have flower-shaped microscopic appearance.By changing the content of sodium-acetate in the electrolytic solution, can adjust microscopic appearance is the ratio of flower-shaped magnesium hydroxide in film.
With traditional glass electrolyzer, ITO is a negative electrode, and platinum electrode is a counter electrode, and saturated calomel electrode (SCE) is a reference electrode.Electrolyte solution is the aqueous solution of 0.1mol/L magnesium nitrate and 0.2mol/L sodium-acetate, and cathode potential is in-1.5V (with respect to SCE), 2 hours time, room temperature.As a comparison, be electrolytic solution with the magnesium nitrate solution that does not contain sodium-acetate, 0.1mol/L magnesium nitrate aqueous solution just, other conditions are identical.The magnesium hydroxide film for preparing carries out Microstructure characterization with XRD and SEM.
The diffraction peak (see figure 1) of the XRD of the film of characterization result demonstration preparation is consistent with the diffraction card of the magnesium hydroxide of standard, illustrates that the both is the film of magnesium hydroxide.But SEM (see figure 2) as a result shows that the microscopic appearance of magnesium hydroxide is flower-shaped crystal from the film of the aqueous solution cathode electrodeposition preparation of 0.1mol/L magnesium nitrate and 0.2 sodium-acetate, and the ratio of flower-shaped crystal in film is 95～100%; And the film that cathode electrodeposition prepares from the 0.1mol/L magnesium nitrate aqueous solution, the microscopic appearance of magnesium hydroxide is the porous network-like structure, does not have flower-like structure.
Embodiment 2
With traditional glass electrolyzer, ITO is a negative electrode, and platinum electrode is a counter electrode, and saturated calomel electrode (SCE) is a reference electrode.Electrolyte solution is the aqueous solution of 0.1mol/L magnesium nitrate and 0.025mol/L sodium-acetate, and cathode potential is in-1.5V (with respect to SCE), 2 hours time, room temperature.
The film of XRD characterization result explanation preparation is a magnesium hydroxide film.SEM (see figure 3) signify hydrogen magnesia film as a result is made up of the magnesium hydroxide and the holey magnesium hydroxide of flower-shaped crystal morphology, and wherein pattern is that flower-shaped crystalline magnesium hydroxide is about 5～7% in the ratio of film.
Embodiment 3
With traditional glass electrolyzer, ITO is a negative electrode, and platinum electrode is a counter electrode, and saturated calomel electrode (SCE) is a reference electrode.Electrolyte solution is the aqueous solution of 0.1mol/L magnesium nitrate and 0.1mol/L sodium-acetate, cathode potential-1.5V (with respect to SCE), 2 hours time, room temperature.
The XRD characterization result shows that the film of cathode electrodeposition preparation is magnesium hydroxide film.SEM (see figure 4) signify hydrogen magnesia film as a result is made up of the magnesium hydroxide and the holey magnesium hydroxide of flower-shaped crystal morphology, and wherein pattern is that flower-shaped crystalline magnesium hydroxide is about 40～60% in the ratio of film.
Embodiment 4
With traditional glass electrolyzer, stainless steel is a negative electrode, and platinum electrode is a counter electrode, and saturated calomel electrode (SCE) is a reference electrode.Electrolyte solution is the aqueous solution of 0.2mol/L magnesium nitrate and 0.15mol/L sodium-acetate, cathode potential-1.5V (with respect to SCE), 1.5 hours time, room temperature.
The XRD characterization result shows that the film of cathode electrodeposition preparation is magnesium hydroxide film.SEM (see figure 5) signify hydrogen magnesia film as a result is made up of the magnesium hydroxide and the holey magnesium hydroxide of flower-shaped crystal morphology, and wherein pattern is that flower-shaped crystalline magnesium hydroxide is about 80～90% in the ratio of film.
Claims (2)
1. one kind contains the preparation method that microscopic appearance is flower-shaped crystalline magnesium hydroxide film, it is characterized in that the aqueous solution with magnesium nitrate and sodium-acetate is electrolytic solution, adopting the cathode electrodeposition method to prepare microscopic appearance is flower-shaped crystalline magnesium hydroxide film, the concentration of magnesium nitrate is at 0.1～0.2mol/L in the described electrolytic solution, and the concentration of sodium-acetate is at 0.025～0.2mol/L.
2. a kind of preparation method that microscopic appearance is flower-shaped crystalline magnesium hydroxide film that contains according to claim 1, the negative electrode that it is characterized in that described employing is indium doped stannum oxide, conductive glass or stainless steel.
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| CN106757247A (en) * | 2016-12-02 | 2017-05-31 | 北京工业大学 | A kind of method of the immobilized flower-shaped magnesium hydroxide of Nano tube array of titanium dioxide |
| CN109137009B (en) * | 2018-09-28 | 2021-02-05 | 北京工业大学 | Method for preparing porous magnesium hydroxide by pulse electrodeposition |
| CN113445097B (en) * | 2021-07-23 | 2022-09-20 | 中国科学院青海盐湖研究所 | Fiber mesh-shaped magnesium oxide film and preparation method and application thereof |
| CN113463156B (en) * | 2021-07-23 | 2022-09-20 | 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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Non-Patent Citations (6)
| Title |
|---|
| Electrosynthesis of Mg(OH)2 coatings on stainlesssteel substrates. M.DINAMANI等.Journal of Applied Electrochemistry,Vol.34 . 2004 |
| Electrosynthesis of Mg(OH)2 coatings on stainlesssteel substrates. M.DINAMANI等.Journal of Applied Electrochemistry,Vol.34 . 2004 * |
| Morphological Control of ZnO Nanostructures byElectrodeposition. Lifen Xu等.The Journal of Physical Chemistry B,Vol.109 No.28. 2005 |
| Morphological Control of ZnO Nanostructures byElectrodeposition. Lifen Xu等.The Journal of Physical Chemistry B,Vol.109 No.28. 2005 * |
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Granted publication date: 20091007 Termination date: 20100929 |