CN103922368A - Preparation method of nano-sheet-based flower-shaped level substructure magnesium hydroxide powder body - Google Patents
Preparation method of nano-sheet-based flower-shaped level substructure magnesium hydroxide powder body Download PDFInfo
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- CN103922368A CN103922368A CN201410163628.3A CN201410163628A CN103922368A CN 103922368 A CN103922368 A CN 103922368A CN 201410163628 A CN201410163628 A CN 201410163628A CN 103922368 A CN103922368 A CN 103922368A
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Abstract
The invention discloses a preparation method of a nano-sheet-based flower-shaped level substructure magnesium hydroxide powder body. The preparation method comprises the steps: dropping a MgSO4 water solution with a concentration of 1.60-1.70 mol/L in an ammonia water solution which is added with a PEG water solution and has a pH value of 11.5-12.5 under the condition of high-speed mixing to obtain a precipitate system, and ageing the precipitate system to obtain a nano-sheet-based flower-shaped level substructure magnesium hydroxide gelatinous precipitate, wherein the adding amounts of all raw materials meet the requirement of a mol ratio of Mg<2+> to OH<-> being 1: 2.4-4.0, and the mass of PEG accounts for 1.2-1.5 percent the total mass of generated Mg(OH)2. The nano-sheet-based flower-shaped level substructure magnesium hydroxide powder body prepared by adopting the preparation method has a specially strong capacity of adsorbing and recovering rare metals from a low-ion concentration solution, and is an environment-friendly efficient retardant.
Description
Technical field
The invention belongs to materials science field, relate to a kind of preparation method of magnesium hydrate powder, particularly a kind of preparation method with the magnesium hydroxide of colored form class aggregated(particle) structure.
Background technology
Magnesium hydroxide is a kind of environment-friendly material, and the adsorptive power in low ion concns solution is very strong.As everyone knows, the specific surface area of sorbent material is larger, and adsorptive power is stronger.Therefore, preparation has compared with the magnesium hydrate powder of bigger serface and has important practical significance.
The specific surface area of flower form class aggregated(particle) structure is all larger than the specific surface area of other any structure.Flower form class aggregated(particle) structure is a kind of secondary structure (secondary level aggregated(particle) structure), can not direct growth out, its primary structure unit is micron or the nanometer sheet that surface has active group.Appeared in the newspapers lead about preparing the most hydrothermal methods that adopt of method of colored form class aggregated(particle) structure, utilize High Temperature High Pressure to change the crystal habit of crystal, to create the structural unit with surface active groups, under suitable pH condition, rely on the complementary group of activity of active group to take on a grade aggregated(particle) structure.
Preparation condition with hydrothermal method preparation flower form class aggregated(particle) structure is not gentle, and the reactant concn adopting in the method for all reports is all less, so output is very little, does not have practical production meaning.
Summary of the invention
The object of this invention is to provide a kind of in the lower method that adopts high reactant concn to prepare the colored form class aggregated(particle) structure magnesium hydrate powder of nanometer sheet base of normal temperature and pressure (non-hydrothermal condition).
Preparation method of the present invention is under rapid stirring, by the MgSO of 1.60～1.70mol/L
4the aqueous solution splashes into be added with in the ammonia soln PEG aqueous solution, pH value 11.5～12.5 and is precipitated system, obtains the colored form class aggregated(particle) structure magnesium hydroxide gelatinous precipitate of nanometer sheet base after precipitation system ageing, and wherein the add-on of various raw materials meets Mg
2+﹕ OH
-be the mol ratio of 1 ﹕ 2.4～4.0, the quality of PEG accounts for the Mg of generation (OH)
21.2～1.5% of total mass.
The PEG adding in the present invention plays finishing and ligand guiding, and the described PEG aqueous solution is preferably respectively 200,6000 and 20000 the PEG aqueous solution being made into soluble in water by the molecular weight of equal in quality.
In above-mentioned preparation method, the digestion time of described precipitation system is 1～2h preferably.
By described gelatinous precipitate with absolute ethanol washing, to without SO
4 2-detect, after being dried, obtain the colored form class aggregated(particle) structure magnesium hydrate powder based on nanometer sheet base.Due to Mg (OH)
2in water, dissolve in a large number, therefore the present invention adopts dehydrated alcohol to wash gelatinous precipitate, in order to avoid washing process causes Mg (OH)
2loss.
The present invention is by adopting above-mentioned preparation method, obtained the colored form class aggregated(particle) structure magnesium hydrate powder of nanometer sheet base, the magnesium hydrate powder of this colored form class aggregated(particle) structure has the ability that rare metal is reclaimed in unique very strong absorption from low ion concns solution, is also a kind of eco-friendly efficient flame-retarding agent.
By JEM2100F type high resolving power transmission electron microscope observing, be scattered in the wet gel that the present invention in dehydrated alcohol spends the magnesium hydrate powder of form class aggregated(particle) structure, its full-resolution picture is as Fig. 1.From figure, can be clear that many nano particles are according to unified crystallographic direction assembling (wherein Fig. 1 b is the amplification of enclosing part in Fig. 1 a) in blocks, the about 3.5nm of nanoparticle size.
This mode is called " orientation is adhered to (Oriented Attachment) ", is a kind of new crystal growth pattern that is different from " slaking (Ostwald Ripening) ".So-called " orientation is adhered to " is to take nano particle as growing element, has the spontaneous assembling process of the adjacent particle of the corner of the eyes of identical crystallographic direction, and the particle of assembling is fused into monocrystalline by face combination.From the viewpoint of thermokinetics, to be high-energy surface match disappearance by bonding to the power that orientation is adhered to, thereby greatly reduce the surface energy of system.Suitable tensio-active agent is the key element that orientation is adhered to.Fig. 1 shows, preparation method of the present invention has obvious directed apposition growth feature, and detailed process is as follows: the non-nucleus of magnesium hydroxide that 1. forms several nanosizeds in containing the aqueous solution of PEG by homogeneous nucleation.2. due to the strong sucking action between organic molecule and inorganic particle, PEG is adsorbed onto non-nucleating surface (term in orientation is adhered to is that PEG catches non-nucleus).3. non-nucleus crystallization, the variation (this process is called " be situated between to see and change ", and its power is that inorganic lattice energy and organic molecule are crooked) that shape and size occur simultaneously becomes temporary transient stable nano particle.The profile of nano particle is little six square pieces (inherent structure by brucite determines), and its side ({ 110}) is that high-energy surface, upper bottom surface ({ 001}) are low energy face.Because system surfaces can be tending towards minimum natural character, PEG is adsorbed on the side (high-energy surface) of little six square pieces.4. except bringing into play basic falling low surface energy effect, more meaningfully, PEG by with Mg (OH)
2between special coordination and the structure-directing effect of ligand in water, made nano grain surface functionalization, that is, the nano particle being wrapped up by PEG is orientated along identical crystallographic direction, then immediately along this direction mutual " adhering to " together, this " adheres to " is bonding action.
Selecting PEG is one of unique distinction of the present invention.Making nano grain surface functionalization is that tensio-active agent adheres to the essential place of middle keying action in orientation, because different tensio-active agents is different from the coordination between different inorganic materials, so be suitable for different inorganic materials, there is the directed tensio-active agent adhering to and there is selectivity.PEG and Mg (OH)
2complement each other.PEG is dibasic alcohol, and the ligand that it provides is two hydroxyls (OH), occurs to have remained appropriate hydroxyl after special coordination with magnesium hydroxide, and this part hydroxyl snugly in water has been brought into play structure-directing effect.Do not have residual hydroxyl or residual hydroxyl too much can not produce structure-directing effect, do not have residual hydroxyl there is no guide frame, when residual hydroxyl is too much, between hydroxyl, is wound around and causes nano particle coagulation mutually.
It is two of unique distinction of the present invention that orientation is adhered to, and it has brought into play the effect of forming a connecting link in the structure of flower form class aggregated(particle) structure: on the one hand, the primary structure unit nanometer sheet of flower form class aggregated(particle) structure by directed apposition growth out; The surface tissue of the nanometer sheet generating on the other hand, provides suitable condition for the assembling between nanometer sheet.The upper and lower surface of nanometer sheet is ({ 001}) face, has Mg on it
2+and O
2-; The residual hydroxyl that has PEG on the side of nanometer sheet.These residual hydroxyls or each other bridging form hydrogen bond, or with ({ 001}) face on O
2-form hydrogen bond.The hydroxyl of bridging makes nanometer sheet form Bian-Bian to connect each other, with the O on ({ 001}) face
2-the hydrogen bond forming makes nanometer sheet form the connection of limit-face.In certain space, continuous hydroxyl makes nanometer sheet be assembled into flower.Owing to also having a small amount of residual hydroxyl on the edge of petal, the flower of the some amount again hydrogen bond by is therebetween gathered into a pile.As shown in Figure 3.
Nanometer sheet is assembled into flower by hydrogen bond, is three of unique distinction of the present invention, and due to hydrogen bond action, nanometer sheet must be assembled into colored shape.
Select ammoniacal liquor to do precipitation agent, because magnesium sulfate relatively relaxes (comparing with sodium hydroxide precipitation agent) with the reaction between ammoniacal liquor, be equivalent to improve the mobility of nanoparticle growth unit, high mobility is that directed prerequisite of adhering to occurs.Therefore, selecting ammoniacal liquor to do precipitation agent is four of unique distinction of the present invention.
Five of unique distinction of the present invention is the reactant solutions that adopted high density.Because the solubleness of magnesium sulfate is high, the reactant solution of configuration high density is possible, and this has established practical basis for industrialization.On the other hand, reaction just can be carried out at normal temperatures and pressures.
Adopt Rigaku Dmax-rB type diffractometer, under voltage 40kv, electric current 100mA condition, with Cu target, K
αray carries out X-ray diffraction analysis to the magnesium hydrate powder obtaining, and obtains the XRD spectrum of Fig. 2 a.Adopt QUANTAX200 energy spectrometer to carry out chemical composition analysis to the magnesium hydrate powder obtaining, obtain the EDS spectrogram of Fig. 2 b.
By the JCPDF card (card 07-0239) of Fig. 2 a and brucite (the mineral formal name used at school of magnesium hydroxide) relatively, diffraction peak is very identical, and peak shape is intact, illustrates that the crystalline structure of magnesium hydroxide is intact.Fig. 2 b shows, prepared powder contains " Mg " and " O " element except " H " element, and the chemical composition that prepared powder is described is Mg (OH)
2, " Pt " element in Fig. 2 b comes from conducting film.
Fig. 3 is the magnesium hydrate powder pattern of observing on S4800 type field emission scanning electron microscope.From Fig. 3 a, prepared powder is to have even beads colored shape outward appearance, grain diameter 2～3 μ m, and a flower (particle) is comprised of tens nanometer sheet, and the bead of some amount is gathered into a pile; From Fig. 3 b, can find out the colored shape lines on bead surface; Fig. 3 c is the pattern of a flower, and what many nanometer sheet were orderly links together, the thick 25～40nm of nanometer sheet; Fig. 3 d is the internal morphology of the further flower amplifying, and therefrom can see between nanometer sheet and linking together by Bian-Bian or limit-face.
Adopt the pattern of TECNAIG2F20 type field transmission electron microscopic observation flower and the deep structure of research flower, as Fig. 4, voltage 200Kv.Fig. 4 a is the transmission electron microscope pattern picture of a flower, and its shape characteristic and Fig. 3 c fit like a glove.Strongly ultrasonic do not break into pieces flower, illustrates that flower is a firmly integral body, rather than the aggregate of nanometer sheet.Fig. 4 b is the electron diffraction picture of a flower, and the feature of concentric ring shows that a flower is polycrystalline.Fig. 4 c-g has shown the constitutional features of a nanometer sheet.The HRTEM pattern picture at a nanometer sheet edge and its diffraction spot explanation nanometer sheet are monocrystalline, and this " orientation is adhered to " growth mechanism of having affirmed again nanometer sheet is correct.
Fig. 5 has provided the overall building schematic diagram of the colored form class aggregated(particle) structure magnesium hydroxide of nanometer sheet base.In figure, (a) non-nucleus; (b) non-nucleus is caught by PEG, and straight line double-headed arrow represents inorganic lattice energy, and curve double-headed arrow represents that organic molecule is crooked; (c) be situated between and see the rear stable hexagonal nano particle of transformation; (d) orientation is adhered to the nanometer sheet of formation; (e) the colored form class aggregated(particle) structure being assembled into by hydrogen bond.
Accompanying drawing explanation
Fig. 1 is the full-resolution picture that magnesium hydroxide gelatinous precipitate that the present invention prepares is dispersed in the directed apposition growth in dehydrated alcohol.
Fig. 2 is XRD figure spectrum and the EDS collection of illustrative plates of the magnesium hydrate powder for preparing of the present invention.
Fig. 3 is the scanning electron microscope pattern picture of the magnesium hydrate powder for preparing of the present invention.
Fig. 4 is the transmission electron microscope pattern picture of the magnesium hydrate powder for preparing of the present invention.
Fig. 5 is the schematic diagram of m of magnesium hydroxide of the colored form class aggregated(particle) structure of nanometer sheet base.
Embodiment
Embodiment 1
Take 20.5g MgSO
4be dissolved in distilled water, be made into 100mL solution.
It is 11.5 ammonia soln that strong aqua is diluted to pH value, gets 182mL, adds each 13.6mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, is made into precipitant solution.
By 30mL MgSO
4solution is added dropwise in above-mentioned precipitant solution under rapid stirring, after dropping finishes, by the still aging 2h of precipitation system.
By the good system suction filtration of ageing, use absolute ethanol washing gelatinous precipitate, wash altogether each 50mL 3 times.With BaCl
2solution check washings, to separating out without white precipitate.
The clean wet gel that takes a morsel is dispersed in dehydrated alcohol, obtains translucent solution, gets it and carries out high resolving power transmission electron microscope (HRTEM) observation.
By remaining clean wet gel 120 ℃ of forced air dryings to absolutely dry, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 2
Take 20.5g MgSO
4be dissolved in distilled water, be made into 100mL solution.
It is 12.0 ammonia soln that strong aqua is diluted to pH value, gets 30.4mL, adds each 13.6mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, is made into precipitant solution.
By 30mL MgSO
4solution is added dropwise in above-mentioned precipitant solution under rapid stirring, after dropping finishes, by the still aging 1.5h of precipitation system.
By the good system suction filtration of ageing, use absolute ethanol washing gelatinous precipitate, wash altogether each 50mL 3 times.With BaCl
2solution check washings, to separating out without white precipitate.To clean wet gel extremely absolutely dry 120 ℃ of forced air dryings, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 3
Take 20.5g MgSO
4be dissolved in distilled water, be made into 100mL solution.
It is 12.5 ammonia soln that strong aqua is diluted to pH value, gets 29.1mL, adds each 27.2mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, is made into precipitant solution.
By 60mL MgSO
4solution is added dropwise in above-mentioned precipitant solution under rapid stirring, after dropping finishes, by the still aging 1h of precipitation system.
By the good system suction filtration of ageing, use absolute ethanol washing gelatinous precipitate, wash altogether each 50mL 3 times.With BaCl
2solution check washings, to separating out without white precipitate.To clean wet gel extremely absolutely dry 120 ℃ of forced air dryings, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 4
Take 19.3g MgSO
4be dissolved in distilled water, be made into 100mL solution.
It is 11.5 ammonia soln that strong aqua is diluted to pH value, gets 171mL, adds each 12.8mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, is made into precipitant solution.
By 30mL MgSO
4solution is added dropwise in above-mentioned precipitant solution under rapid stirring, after dropping finishes, by the still aging 2h of precipitation system.
By the good system suction filtration of ageing, use absolute ethanol washing gelatinous precipitate, wash altogether each 45mL 3 times.With BaCl
2solution check washings, to separating out without white precipitate, will clean wet gel extremely absolutely dry 120 ℃ of forced air dryings, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 5
Take 19.3g MgSO
4be dissolved in distilled water, be made into 100mL solution.
It is 11.5 ammonia soln that strong aqua is diluted to pH value, gets 28.6mL, adds each 12.8mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, is made into precipitant solution.
By 30mL MgSO
4solution is added dropwise in above-mentioned precipitant solution under rapid stirring, after dropping finishes, by the still aging 1.5h of precipitation system.
By the good system suction filtration of ageing, use absolute ethanol washing gelatinous precipitate, wash altogether each 45mL 3 times.With BaCl
2solution check washings, to separating out without white precipitate, will clean wet gel extremely absolutely dry 120 ℃ of forced air dryings, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Claims (3)
1. a preparation method for the colored form class aggregated(particle) structure magnesium hydrate powder of nanometer sheet base, is under rapid stirring, by the MgSO of 1.60～1.70mol/L
4the aqueous solution splashes into be added with in the ammonia soln PEG aqueous solution, pH value 11.5～12.5 and is precipitated system, obtains the colored form class aggregated(particle) structure magnesium hydroxide gelatinous precipitate of nanometer sheet base after precipitation system ageing, and wherein the add-on of various raw materials meets Mg
2+﹕ OH
-be the mol ratio of 1 ﹕ 2.4～4.0, the quality of PEG accounts for the Mg of generation (OH)
21.2～1.5% of total mass.
2. preparation method according to claim 1, is characterized in that the described PEG aqueous solution is respectively 200,6000 and 20000 soluble in water being made into of PEG by the molecular weight of equal in quality.
3. preparation method according to claim 1, the digestion time that it is characterized in that described precipitation system is 1～2h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105197967A (en) * | 2015-09-17 | 2015-12-30 | 南昌大学 | Preparation method of flower-like magnesium oxide loaded with transition metal oxide |
| CN116835616A (en) * | 2023-08-30 | 2023-10-03 | 山东艾科高分子材料有限公司 | Method for preparing high-dispersion hexagonal flaky magnesium hydroxide by high-activity light-burned magnesium oxide through one-step hydrothermal method |
Citations (1)
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|---|---|---|---|---|
| CN1458066A (en) * | 2002-05-17 | 2003-11-26 | 隗学礼 | Process for preparing magnesium hydroxide whisker |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458066A (en) * | 2002-05-17 | 2003-11-26 | 隗学礼 | Process for preparing magnesium hydroxide whisker |
Non-Patent Citations (4)
| Title |
|---|
| A. PILARSKA等: "SYNTHESIS OF Mg(OH)2 FROM MAGNESIUM SALTS AND NH4OH BY DIRECT FUNCTIONALISATION WITH POLY(ETHYLENE GLYCOLS)", 《PHYSICOCHEMICAL PROBLEMS OF MINERAL PROCESSING》, vol. 48, no. 2, 31 December 2012 (2012-12-31), pages 631 - 643 * |
| CHENGLIN YAN等: "Preparation of magnesium hydroxide nanoflowers", 《JOURNAL OF CRYSTAL GROWTH》, vol. 282, 14 July 2005 (2005-07-14), pages 448 - 454 * |
| XIAOHONG PAN等: "Investigation of Antibacterial Activity and Related Mechanism of a Series of Nano-Mg(OH)2", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 5, 9 January 2013 (2013-01-09), pages 1137 - 1142 * |
| 孙灵娜等: "Mg(OH)2纳米晶的可控制备", 《深圳大学学报理工版》, vol. 30, no. 2, 31 March 2013 (2013-03-31), pages 205 - 209 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105197967A (en) * | 2015-09-17 | 2015-12-30 | 南昌大学 | Preparation method of flower-like magnesium oxide loaded with transition metal oxide |
| CN106064829A (en) * | 2015-09-17 | 2016-11-02 | 南昌大学 | A kind of preparation method of the flower-shaped magnesium oxide of carrying tin oxide |
| CN106064829B (en) * | 2015-09-17 | 2017-11-03 | 南昌大学 | A kind of preparation method of the flower-shaped magnesia of carrying tin oxide |
| CN116835616A (en) * | 2023-08-30 | 2023-10-03 | 山东艾科高分子材料有限公司 | Method for preparing high-dispersion hexagonal flaky magnesium hydroxide by high-activity light-burned magnesium oxide through one-step hydrothermal method |
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