CN105036200B - Preparation method for layered double hydroxide (LDH) nanoscrolls - Google Patents
Preparation method for layered double hydroxide (LDH) nanoscrolls Download PDFInfo
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Abstract
The invention discloses a preparation method for layered double hydroxide (LDH) nanoscrolls. The preparation method specifically comprises the following steps: uniformly mixing a cationic surface active agent, a cosurfactant and an alkanes oil phase at room temperature to obtain a uniform and stable emulsus suspension system; then mixing a soluble bivalent metal salt and a soluble trivalent metal salt with deionized water, and adding the mixture to the emulsus suspension system to obtain a microemulsion system; and finally mixing an alkaline substance with deionized water, then adding the mixture to the microemulsion system, continuously stirring for 0.5-5 hours, and carrying out a hydrothermal reaction at 75-130 DEG C for 2-60 hours to obtain the LDH nanoscrolls. According to the preparation method disclosed by the invention, oligolamellar LDH is generated by means of the mutual action of LDH growth units and a drop film interface under a microemulsion condition, and is further folded to form the LDH nanoscrolls. The preparation method disclosed by the invention is mild in reaction conditions, simple and feasible and short in time consumption; the LDH nanoscrolls synthesized by the preparation method are regular in shape and favorable in dispersity.
Description
Technical field
The present invention relates to the preparation field of inorganic material and in particular to a kind of layered duplex metal hydroxide nanometer volume system
Preparation Method.
Background technology
Layered double hydroxide (layered double hydroxides, be abbreviated as ldh) is that a class interlayer has
The hydrotalcite-based compound of exchangeable anions, composition is represented by the formula: [m2+ 1-xm3+ x(oh)2](an-)x/n·mh2O,
Wherein m2+、m3+It is in divalence and the trivalent metal cation of main layer board octahedral interstices, a respectivelyn-It is in alkaline solution
Can stable existence the anion positioned at interlayer.There is strong covalent bond, interlayer is between the main layer board of double-metal hydroxide
A kind of weak interaction force, passes through hydrogen bond, Van der Waals force, electrostatic force etc. and combines between Subjective and Objective.
Layered double hydroxide has multielement, the supramolecular structure of many of bondings, catalysis, absorption, industry fire-retardant,
The various fields such as medical industry, environmental project, functional high molecule material show huge application prospect.However, by routine
The ldh that Co deposited synthesis go out reunites seriously, assembles easily in macromolecule matrix, and then affects the comprehensive of composite
Energy.For overcoming drawbacks described above and obtaining high-performance composite materials, lift-off processing need to be carried out to ldh.It is related to ldh at present and peel off knot
The research of structure focuses primarily upon, by the method for ion exchange or calcining reduction, organic or inorganic anion is introduced ldh interlayer,
Reduce the active force between laminate, under the effect of stronger external force, finally obtain the lamella of stripping.But aforesaid operations take long and logical
Often it is related to the use of toxic solvent, big for environment pollution.Compared with method before this, by pattern control, directly preparation is in polymer
In matrix, a kind of finely disseminated ldh of new structure is very necessary.
With regard to layered double hydroxide controllable standby, in now studies have reported that, Hu wait (gang hu, dermot
O ' hare.j.am.chem.soc., 2005,127:17808～17813) by adding polymer masterplate in microemulsion system
Prepare banding and bar-shaped ldh respectively, but the stacking between ldh lamella is than more serious.Liu etc. (chunxia liu,
Wangaohou.j.disper.sci.technol.2009,30:174～177) by add chelating agent control ldh nucleation and
The release of metal ion in crystallization process, prepares ring-type, spherical and fibrous ldh, but finds that ldh still deposits in tem in figure
In more serious agglomeration.(yun zhao, qingze rao, the xuejia ding.chem.res.chinese such as Zhao
U.2007,23:622～624) utilize hydro-thermal method, synthesize ldh nano wire at 190 DEG C, product is regular and dispersed preferable.
But this method reaction temperature is too high, power consumption is larger and has certain risk.
Content of the invention
The invention provides a kind of preparation method of layered duplex metal hydroxide nanometer volume, pass through under miniemulsion conditions
Ldh growth unit generates few layer ldh with the interaction of drop membrane interface, and then folds formation ldh nanometer roll.The method is reacted
Mild condition, simple, time-consuming short, the ldh nanometer roll-shape synthesizing is regular, favorable dispersibility.
A kind of preparation method of layered duplex metal hydroxide nanometer volume, comprises the steps:
(1) cationic surfactant, cosurfactant and alkanes oil phase are mixed at room temperature, obtain
The milky suspension system of stable homogeneous；
(2) soluble divalent metal salt and soluble trivalent metal salt are mixed to get salting liquid with deionized water, add
In the milky suspension system obtaining to step (1), obtain microemulsion system；
(3) alkaline matter is mixed with deionized water, be then added in the microemulsion system that step (2) obtains, persistently stir
After mixing 0.5～5h, then through hydro-thermal reaction 2～60h at 75～130 DEG C, obtain described layered duplex metal hydroxide nanometer volume；
Described alkaline matter is urea or ammoniacal liquor.
In the present invention layered duplex metal hydroxide nanometer volume prepare under miniemulsion conditions, surfactant with
The use of cosurfactant can substantially reduce oil/water interfacial tension, contributes to forming stable microemulsion system.Reaction system
The concentration that middle slaine adds is relatively low, is effectively reduced stacking in growth course for the ldh, is conducive to the control of ldh pattern.
Preferably,
Described alkanes oil phase and total deionized water volume ratio are 1:0.03～1；
The molal weight of described surfactant and total deionized water is than for 1:5～60；
Described cosurfactant is 1:0.3～6 with the volume ratio of total deionized water；
Described total deionized water is step (2) and step (3) institute deionized water summation.
Preferably, described alkanes oil phase is n-hexane, normal heptane, normal octane, hexamethylene or oleyl amine；
Described cationic surfactant be Cetyltrimethylammonium bromide, OTAC, ten
Six alkyl trimethyl ammonium bromides, hexadecyltrimethylammonium chloride, TTAB, tetradecyltrimethylammonium chlorine
Change ammonium, DTAB, DTAC, dodecyl benzyl dimethyl ammonium chloride, 14
Zephiran, cetalkonium chloride or stearyl dimethyl benzyl ammonium chloride；
Described cosurfactant is n-butanol, n-amyl alcohol, n-hexyl alcohol or n-heptanol.
It has been investigated that, using the shorter oil molecule of the longer surfactant of carbon chain lengths and carbon chain lengths, exist simultaneously
The formation of water-in-oil microemulsion can be promoted in the presence of the more low-carbon alcohols of content.
Further preferred:
Described alkanes oil phase and total deionized water volume ratio are 1:0.15～0.5.Find, oil-water ratio is (i.e. through test
The volume ratio of alkanes oil phase and total deionized water) too small when, the contact with each other during the course of the reaction probability of collision of drop increases,
Stacking between ldh also can increased, and oil-water ratio is too small to also result in pressure drop in course of reaction, and then leads to ldh volume
Bent incomplete, the phenomenon that coil structure and layer structure coexist therefore occurs；When system profit is excessive, reaction pressure rises bright
Aobvious, ldh dehydration oxidation leads to its structure to change, simultaneously oil-water ratio excessive so that drop size reduces, the ldh piece synthesizing
Layer yardstick is less, and rigidity is relatively large, is unfavorable for crimping.
The molal weight of described surfactant and total deionized water is than for 1:10～36；
Described cosurfactant is 1:0.6～3 with the volume ratio of total deionized water.
Surfactant can be impacted to the stability of reaction system with the consumption of cosurfactant, when both use
When measuring too low, microemulsion system is not sufficiently stable.
Preferably, the bivalent metal ion in described soluble divalent metal salt is co2+、zn2+、ni2+、mg2+In
One or two；
Trivalent metal ion in described soluble trivalent metal salt is al3+、fe3+、cr3+One of or two kinds；
Described soluble divalent metal salt, the anion of soluble trivalent metal salt are cl-、no3 -、so4 2-One of
Or two kinds.Preferably the soluble divalent metal salt of mentioned kind, soluble trivalent metal salt are conducive to preparation crystallization perfect
ldh.
Further preferably, in step (2), soluble divalent metal salt and soluble trivalent metal salt in described salting liquid
Total concentration is 0.01～1mol/l, and the molal weight of soluble divalent metal salt and soluble trivalent metal salt ratio is for 0.5～5:
1, the molal weight of soluble divalent metal salt and soluble trivalent metal salt total amount and alkaline matter is than for 1:1～10.Reaction
In system, ionizable metal salt concentration is crossed conference and leads to the stacking degree between ldh lamella to increase, and coil structure and layer therefore
The phenomenon that shape structure coexists.
Preferably, described alkaline matter is urea or ammoniacal liquor.Using above-mentioned alkaline matter, can be during the course of the reaction
Slow release hydroxyl, the precipitation for metal ion provides necessary alkaline environment, makes ldh growth unit have sufficient time and liquid
Drop film interfacial interaction.
Preferably, the temperature of described hydro-thermal reaction is 105～120 DEG C, the time is 8～20h.Preferably hydro-thermal reaction bar
Part advantageously forms the regular ldh nanometer roll of shape.Temperature is too low to be unfavorable for that alkaline matter decomposes, and the too high ldh of temperature can occur
Oxidation, its coil structure can be destroyed；Need to control the hydro-thermal time in 2～60h, short coil structure is formed the hydro-thermal time simultaneously
Not exclusively, then ldh's hydro-thermal time length reunites seriously, and coil structure also can be destroyed.
The product obtaining after hydro-thermal reaction is again through eccentric cleaning, freeze-drying, you can obtain described layered bi-metal
Hydroxide nano is rolled up.
Compared with prior art, the present invention has the advantage that
1st, microemulsion system of the present invention is sufficiently stable.During synthesis ldh nanometer roll, alkaline matter is slow
Decompose and hydroxyl is provided, the ldh growth unit subsequently forming can be produced with drop membrane interface by electrostatic force and interact, thus
Control ldh to grow along drop membrane interface, be prevented effectively from stacking in growth course for the ldh and reunion.In uniform temperature and
Under pressure condition, the flake widow layer ldh in system is to reduce energy to be stacked with itself, and then can curl into one-dimensional
Structure.Not only specific surface area is big for the ldh nanometer roll of this one-dimentional structure, and easily disperses, and receives for preparing high-performance polymer
Nano composite material provides guarantee.
2nd, analyzed by x-ray diffraction, the degree of crystallinity of the layered duplex metal hydroxide nanometer volume that the present invention prepares
Height, crystal formation is complete, and impurity is few.By transmission electron microscope analysis, the layered duplex metal hydroxide nanometer volume that the present invention prepares
Good dispersion, is difficult to stack, and its length and diameter are respectively 0.5～3 μm and 20～70nm.
Brief description
Fig. 1 is the xrd figure of the layered duplex metal hydroxide nanometer volume of embodiment 1 preparation；
Fig. 2 is the tem figure of the layered duplex metal hydroxide nanometer volume of embodiment 1 preparation；
Fig. 3 is the tem figure of the layered duplex metal hydroxide nanometer volume of embodiment 2 preparation；
Fig. 4 is the xrd figure of the layered duplex metal hydroxide nanometer volume of embodiment 3 preparation；
Fig. 5 is the tem figure of the layered duplex metal hydroxide nanometer volume of embodiment 3 preparation；
Fig. 6 is the tem figure of the layered double hydroxide of comparative example 2 preparation；
Fig. 7 is the tem figure of the layered double hydroxide of comparative example 4 preparation.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1:
In 11ml n-hexyl alcohol, add 11g cetyl trimethylammonium bromide stirring and dissolving.50ml is added in this system
N-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.105g coso4With 0.04g al2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 5ml deionized water, add 0.27g urea, be added drop-wise to above-mentioned system continuously stirred 1h after dissolving, obtain clear
Clear bright microemulsion system.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 95 DEG C of crystallization 12h.Reaction end treats it
Take out after being down to room temperature, use ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen-oxygen
Compound.
The xrd spectrogram of the layered double hydroxide that the present embodiment is obtained is as shown in Figure 1.As can be seen that curve baseline
Steadily, the characteristic peak positions of product diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak
Sharply, illustrate really to have synthesized layered double hydroxide, and its symmetry is good, degree of crystallinity is higher.
The tem photo of layered double hydroxide manufactured in the present embodiment is as shown in Fig. 2 it can be seen that produce
There are stratiform and two kinds of structures of web-like in thing, the wherein length of nanometer roll is 1～3 μm.Reaction temperature is that when 95 DEG C, system pressure is inclined
Little, lead to portion of product not curl into one-dimentional structure from layer structure.
Embodiment 2:
In 11ml n-hexyl alcohol, add 11g cetalkonium chloride stirring and dissolving.Add in this system
50ml n-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.105g coso4With 0.04g al2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 5ml deionized water, add 0.27g urea, be added drop-wise to above-mentioned system continuously stirred 3h after dissolving, obtain clear
Clear bright microemulsion system.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 15h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen
Oxide.
The xrd spectrogram of layered duplex metal hydroxide nanometer volume manufactured in the present embodiment is similar to that shown in Fig. 1, and baseline is put down
Surely, the characteristic peak positions that product diffraction maximum position and layered double hydroxide are received are coincide, and (003) and (006) two peak
Sharply, symmetry is good, shows layered double hydroxide perfect crystalline and the degree of crystallinity height synthesizing.
The tem photo of layered duplex metal hydroxide nanometer volume manufactured in the present embodiment is as shown in Figure 3.As can be seen that producing
Thing is substantially all as nanometer volume structure, and shape is regular and good dispersion, its length and diameter be respectively 0.5～2 μm and 20～
70nm.
Embodiment 3:
In 11ml n-hexyl alcohol, add 12g tetradecyl dimethyl benzyl ammonium stirring and dissolving.Add in this system
50ml n-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 15ml deionized water, add 0.105g coso4With 0.04g al2(so4)3, it is added drop-wise to after stirring and dissolving
State suspension system.In 5ml deionized water, add 0.27g urea, be added drop-wise to above-mentioned system continuously stirred 1h after dissolving, obtain
Microemulsion system to clear.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 125 DEG C of crystallization 30h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen
Oxide.
The xrd spectrogram of layered double hydroxide manufactured in the present embodiment is as shown in figure 4, it can be seen that produce
Though thing shows the characteristic diffraction peak in (003) and (006) two crystal face for the layered double hydroxide, have also appeared simultaneously
Many miscellaneous peaks.These miscellaneous peaks belong to the diffraction maximum of cobalt oxide and aluminum oxide, illustrate with reaction temperature rising, crystallization time
Length easily makes ldh dehydration oxidation.
The tem photo of layered double hydroxide manufactured in the present embodiment is as shown in Figure 5.As can be seen that product is almost
There is not a nanometer volume structure, substantially with 1～2 μm of little aggregate structure composition, between little aggregation, contact is formed each other
Larger aggregate.This phenomenon shows that temperature rises, and microemulsion system is unstable, and ldh easily aoxidizes and mutually assembles, and is difficult
Form coiled structure.
Embodiment 4:
In 11ml n-amyl alcohol, add 11g cetyl trimethylammonium bromide stirring and dissolving.50ml is added in this system
N-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.105g coso4With 0.04g al2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 5ml deionized water, add 0.27g urea, be added drop-wise to above-mentioned system continuously stirred 1.5h after dissolving, obtain
The microemulsion system of clear.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 3h.Reaction end treats it
Take out after being down to room temperature, use ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen-oxygen
Compound.
The xrd spectrogram of layered double hydroxide manufactured in the present embodiment is similar to that shown in Fig. 1, can from figure
Go out, baseline steadily, coincide by the characteristic peak positions of product diffraction maximum position and layered double hydroxide, but (003) and (006)
Two peaks are less sharp, show that the layered double hydroxide crystallization synthesizing is general, illustrate that crystallization time is ldh during 3h
Crystallization still imperfection.
It is 3h that the tem photo of the layered double hydroxide prepared by from the present embodiment can be seen that when crystallization time
When, the amount of crimp of ldh is not high, is in the state of volume one and half, and that is, a part for ldh lamella has crimped and completed, another portion
Divide and keep layer structure, ldh is still presented in little aggregation.This phenomenon show the curling behavior of ldh be one progressive
One-dimentional structure after the completion of process, and curling is more easy to disperse compared with layer structure.
Embodiment 5:
In 11ml n-hexyl alcohol, add 11g OTAC stirring and dissolving.50ml is added in this system
Oleyl amine simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.105g coso4With 0.04g al2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 5ml deionized water, add 0.27g urea, be added drop-wise to above-mentioned system continuously stirred 1h after dissolving, obtain
The microemulsion system of clear.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 48h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen
Oxide.
The xrd spectrogram of layered double hydroxide manufactured in the present embodiment is similar to that shown in Fig. 4.As can be seen that product
Though showing the characteristic diffraction peak in (003) and (006) two crystal face for the layered double hydroxide, have also appeared perhaps simultaneously
Many miscellaneous peaks.These miscellaneous peaks belong to the diffraction maximum of cobalt oxide and aluminum oxide, illustrate at a certain temperature, to prolong with crystallization time
Long ldh is easily dehydrated oxidation.
The tem photo of layered double hydroxide manufactured in the present embodiment is similar to that shown in Fig. 5.As can be seen that product
There's almost no a nanometer volume structure, substantially with 1～2 μm of little aggregate structure composition, contact each other between little aggregation
Define larger aggregate.This phenomenon shows at a certain temperature, to extend ldh with crystallization time and easily aoxidize and mutually interpolymerized
Collection, leads to its structure to change, again becomes layer structure again.
Embodiment 6:
In 15ml n-butanol, add 5g TTAB stirring and dissolving.45ml is added in this system
N-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.1gzncl2With 0.03g fecl3, after stirring and dissolving, it is added drop-wise to above-mentioned suspended substance
System.Continue dropping 5ml ammoniacal liquor (concentration is 20%) continuously stirred 1h, obtain the microemulsion system of clear.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 100 DEG C of crystallization 24h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen
Oxide.
The xrd spectrogram of layered double hydroxide prepared by the present embodiment is similar to that shown in Fig. 1.Baseline is steady, product
The characteristic peak positions of diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak are sharply, symmetrically
Property good, show the layered double hydroxide perfect crystalline that synthesizes and degree of crystallinity be high.
The tem photo of layered double hydroxide manufactured in the present embodiment is similar to that shown in Fig. 2, can from figure
Go out, product has stratiform and two kinds of structures of web-like, the wherein length of nanometer roll is 1～2 μm.This phenomenon is probably to live in surface
Property agent addition is less, and microemulsion system is not sufficiently stable.Additionally, reaction temperature is that when 100 DEG C, system pressure is less than normal, also lead to portion
Product is divided not curl into one-dimentional structure from layer structure.
Embodiment 7:
In 10ml n-butanol, add 18g DTAC stirring and dissolving.60ml is added in this system
Normal heptane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.21g mg (no3)2With 0.08g fe (no3)3, it is added drop-wise to after stirring and dissolving
State suspension system.Continue dropping 5ml ammoniacal liquor (concentration is 20%) continuously stirred 2h, obtain the microemulsion system of clear.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 12h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen
Oxide.
The xrd spectrogram of layered double hydroxide prepared by the present embodiment is similar to that shown in Fig. 1.Curve baseline is steady,
The characteristic peak positions of product diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak are sharply,
Show layered double hydroxide perfect crystalline and the degree of crystallinity height synthesizing.
The tem photo of the layered duplex metal hydroxide nanometer volume prepared by from the present embodiment can be seen that with reaction
The lifting of ionizable metal salt concentration, the stacking degree between ldh lamella can accordingly increase, and coil structure therefore and tie with stratiform
The length of the phenomenon that structure coexists, wherein coil structure and diameter are respectively 0.5～2 μm and 20～90nm.
Embodiment 8:
In 5ml n-hexyl alcohol, add 13g cetyl trimethylammonium bromide stirring and dissolving.40ml is added in this system
Normal octane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 20ml deionized water, add 0.2g coso4With 0.15g fe2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 5ml deionized water, add 0.27g urea, be added drop-wise to above-mentioned system continuously stirred 2h after dissolving, obtain clear
Clear bright microemulsion system.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 8h.Reaction end treats it
Take out after being down to room temperature, use ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen-oxygen
Compound.
The xrd spectrogram of layered double hydroxide prepared by the present embodiment is similar to that shown in Fig. 1.Baseline is steady, product
The characteristic peak positions of diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak are sharply, symmetrically
Property good, show the layered double hydroxide perfect crystalline that synthesizes and degree of crystallinity be high.
The tem photo of the layered double hydroxide prepared by from the present embodiment can be seen that works as cosurfactant
When addition is less, microemulsion system is not sufficiently stable, and the phenomenon that coil structure and layer structure coexist, wherein coil structure
Length and diameter be respectively 1～3 μm and 50～90nm.
Embodiment 9:
In 15ml n-hexyl alcohol, add 18g cetyl trimethylammonium bromide stirring and dissolving.50ml is added in this system
N-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 40ml deionized water, add 0.4g niso4With 0.1g cr2(so4)3, it is added drop-wise to above-mentioned outstanding after stirring and dissolving
Buoyancy aid system.In 10ml deionized water, add 0.6g urea, be added drop-wise to above-mentioned system continuously stirred 3h after dissolving, obtain clear
Clear bright microemulsion system.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 12h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, and last freeze-drying obtains the double gold of stratiform
Belong to hydroxide.
The xrd spectrogram of layered double hydroxide prepared by the present embodiment is similar to that shown in Fig. 1.Baseline is steady, product
The characteristic peak positions of diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak are sharply, symmetrically
Property good, show the layered double hydroxide perfect crystalline that synthesizes and degree of crystallinity be high.
The tem photo of the layered double hydroxide prepared by from the present embodiment can be seen that and subtracts when system oil-water ratio
Hour, the contact with each other during the course of the reaction probability of collision of drop increases, and the stacking between ldh also can increased.Meanwhile, exist
At identical temperature, oil-water ratio reduces and means system pressure drop during the course of the reaction, also results in ldh curling not exclusively, because
The phenomenon that coil structure and layer structure coexist, the wherein length of coil structure and diameter and is respectively 0.5～2 μm and 50 in this
～130nm.
Embodiment 10:
In 9ml n-hexyl alcohol, add 10g cetyl trimethylammonium bromide stirring and dissolving.40ml is added in this system
Hexamethylene simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 2.5ml deionized water, add 0.05g coso4With 0.06g al2(so4)3, it is added drop-wise to after stirring and dissolving
State suspension system.In 2.5ml deionized water, add 0.05g urea, after dissolving, be added drop-wise to above-mentioned system continuously stirred 1h,
Obtain the microemulsion system of clear.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 10h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying is to layered bi-metal hydrogen
Oxide.
The xrd spectrogram of layered double hydroxide prepared by the present embodiment is similar to that shown in Fig. 4.Can from figure
Go out, though product shows the characteristic diffraction peak in (003) and (006) two crystal face for the layered double hydroxide, also simultaneously
Occur in that many miscellaneous peaks.These miscellaneous peaks belong to the diffraction maximum of cobalt oxide and aluminum oxide, and the reaction when oil-water ratio increases is described
The pressure of system can accordingly increase, and leads to ldh dehydration oxidation.
It is substantially layer that the tem photo of the layered double hydroxide prepared by from the present embodiment can be seen that product
Shape structure.This is because its reaction pressure rises substantially when system oil-water ratio increases, ldh dehydration oxidation leads to its structure to occur
Change.Oil-water ratio increases simultaneously means that drop size reduces, and the ldh lamella yardstick synthesizing is less, and rigidity is relatively large, no
Beneficial to curling.
Embodiment 11:
In 8ml n-heptanol, add 8g cetyl dimethyl benzyl ammonium bromide stirring and dissolving.Add in this system
40ml n-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 2.5ml deionized water, add 0.1g coso4With 0.05g al2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 2.5ml deionized water, add 0.2g urea, be added drop-wise to above-mentioned system continuously stirred 1h after dissolving, obtain
The microemulsion system of clear.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 12h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen
Oxide.
The xrd spectrogram of layered double hydroxide prepared by the present embodiment is similar to that shown in Fig. 4.Can from figure
Go out, though product shows the characteristic diffraction peak in (003) and (006) two crystal face for the layered double hydroxide, also simultaneously
Occur in that many miscellaneous peaks.These miscellaneous peaks belong to the diffraction maximum of cobalt oxide and aluminum oxide, and the reaction when oil-water ratio increases is described
The pressure of system can accordingly increase, and leads to ldh dehydration oxidation.
It is substantially layer that the tem photo of the layered double hydroxide prepared by from the present embodiment can be seen that product
Shape structure.This is because its reaction pressure rises substantially when system oil-water ratio increases, ldh dehydration oxidation leads to its structure to occur
Change.Oil-water ratio increases simultaneously means that drop size reduces, and the ldh lamella yardstick synthesizing is less, and rigidity is relatively large, no
Beneficial to curling.Compared with embodiment 10 synthetic product, the amount of crimp that the present embodiment prepares product substantially increases, and illustrates to improve
Reactant concentration can reduce reaction pressure to a certain extent.
Embodiment 12:
In 11ml n-hexyl alcohol, add 11g Cetyltrimethylammonium bromide stirring and dissolving.50ml is added in this system
N-hexane simultaneously stirs 30min, obtains the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.12g coso4With 0.05g al2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 5ml deionized water, add 0.3g urea, be added drop-wise to above-mentioned system continuously stirred 1h after dissolving, obtain clear
Clear bright microemulsion system.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 85 DEG C of crystallization 60h.Reaction end treats it
Take out after being down to room temperature, use ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen-oxygen
Compound.
The xrd spectrogram of layered double hydroxide manufactured in the present embodiment is similar to that shown in Fig. 1.Can from figure
Go out, curve baseline steadily, coincide by the characteristic peak positions of product diffraction maximum position and layered double hydroxide, and (003) and
(006) two peak is sharp, illustrates really to have synthesized layered double hydroxide, and its symmetry is good, degree of crystallinity is higher.
The tem photo of layered double hydroxide manufactured in the present embodiment is similar to that shown in Fig. 2.Can from figure
Go out, product has stratiform and two kinds of structures of web-like, the wherein length of nanometer roll is 1～3 μm.Reaction temperature is system pressure when 80 DEG C
Power is less than normal, leads to portion of product not curl into one-dimentional structure from layer structure.Compared with embodiment 1 synthetic product, this reality
Applying example and preparing the coil structure of product substantially increases, and illustrates to extend the curling of ldh under relatively low reaction pressure with the reaction time
Degree can increased.
Comparative example 1:
In 10ml n-hexyl alcohol, add 10g lauryl sodium sulfate stirring and dissolving.50ml n-hexane is added in this system
And stir 30min, obtain the milky suspension system of stable homogeneous.
In 5ml deionized water, add 0.12g coso4With 0.05g al2(so4)3, it is added drop-wise to above-mentioned after stirring and dissolving
Suspension system.In 5ml deionized water, add 0.3g urea, be added drop-wise to above-mentioned system continuously stirred 1h after dissolving, obtain clear
Clear bright microemulsion system.
Above-mentioned microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 12h.Reaction end is treated
It takes out after being down to room temperature, uses ethanol and deionized water eccentric cleaning for several times respectively, last freeze-drying obtains layered bi-metal hydrogen
Oxide.
The xrd spectrogram of the layered double hydroxide of this comparative example preparation is similar to that shown in Fig. 1.Can from figure
Go out, curve baseline steadily, coincide by the characteristic peak positions of product diffraction maximum position and layered double hydroxide, and (003) and
(006) two peak is sharp, illustrates really to have synthesized layered double hydroxide, and its symmetry is good, degree of crystallinity is higher.
It is substantially layer that the tem photo of the layered double hydroxide prepared by from this comparative example can be seen that product
Shape structure, and there are two kinds of Size Distribution.Essentially 0.5～0.8 μm of the size of big lamella, little lamella 20～50nm it
Between.This phenomenon occurs and is because that the drop membrane interface being formed as surfactant by sds is electronegative, ldh grows base
Unit is also all negative electricity, and both have Coulomb repulsion, and therefore ldh is unrestricted when growing in this microreactor of drop, as
Crystallization growth in common hydrothermal system, thus small size stratiform ldh occurs.In addition, during the course of the reaction can be constantly between drop
Collision carries out mass exchange, thus generating large-size ldh.
Comparative example 2
In 40ml deionized water, add 0.84g coso4With 0.328g al2(so4)3, stirring and dissolving；40ml go from
In sub- water, add 0.5g NaOH, stirring and dissolving.Both rapid stirrings in water heating kettle are mixed, then moves into 110 DEG C of bakings
Case crystallization 12h, reaction end is down to after room temperature after it and is taken out, and uses ethanol and deionized water eccentric cleaning for several times respectively, finally cold
Lyophilized dry layered double hydroxide.
In this comparative example, the xrd spectrogram of prepared layered double hydroxide is similar to that shown in Fig. 1.Baseline steadily, produces
The characteristic peak positions of thing diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak are sharply, right
Title property is good, shows layered double hydroxide perfect crystalline and the degree of crystallinity height synthesizing.
In this comparative example, the tem photo of the layered double hydroxide of preparation is as shown in Figure 6.It can be seen that
Product be yardstick 30～60nm about ldh nanometer sheet, there is not coiled structure, illustrate under hydrothermal conditions using NaOH
Ldh nanometer roll cannot be obtained as alkaline matter.
Comparative example 3
In 40ml deionized water, add 0.84g coso4With 0.328g al2(so4)3, stirring and dissolving；40ml go from
In sub- water, add 2.16g urea, stirring and dissolving.Both rapid stirrings in water heating kettle are mixed, then moves into 110 DEG C of baking ovens
Crystallization 12h, reaction end is down to after room temperature after it and is taken out, and uses ethanol and deionized water eccentric cleaning for several times respectively, finally freezes
Dry layered double hydroxide.
In this comparative example, the xrd spectrogram of prepared layered double hydroxide is similar to that shown in Fig. 1.Baseline steadily, produces
The characteristic peak positions of thing diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak are sharply, right
Title property is good, shows layered double hydroxide perfect crystalline and the degree of crystallinity height synthesizing.
From this comparative example, the tem photo of prepared layered double hydroxide can be seen that product and there is web-like
With two kinds of structures of stratiform, the ldh of two kinds of structures mutually piles up in system, gathering, and wherein the length of coil structure and diameter divide
Wei 0.5～1.5 μm and 20～50nm.This phenomenon shows under a certain pressure, to be used urea can obtain as alkaline matter
Nanometer roll, but its dispersiveness is poor, there is a number of layer structure simultaneously, and the use of microemulsion system can ensure that conjunction
Become homogeneous regular and finely disseminated nanometer roll.
Comparative example 4
In 40ml deionized water, add 0.84g coso4With 0.328g al2(so4)3, stirring and dissolving；40ml go from
In sub- water, add 2.16g urea, stirring and dissolving.Both rapid stirrings in three-neck flask are mixed, is then transferred to oil bath pan
Crystallization 24h at 100 DEG C, reaction end is down to after room temperature after it and is taken out, and uses ethanol and deionized water eccentric cleaning for several times respectively,
Last freeze-drying obtains layered double hydroxide.
In this comparative example, the xrd spectrogram of prepared layered double hydroxide is similar to that shown in Fig. 1.Baseline steadily, produces
The characteristic peak positions of thing diffraction maximum position and layered double hydroxide are coincide, and (003) and (006) two peak are sharply, right
Title property is good, shows layered double hydroxide perfect crystalline and the degree of crystallinity height synthesizing.
In this comparative example, the tem photo of the layered double hydroxide of preparation is as shown in Figure 7.It can be seen that
Product is the ldh micron film of 2～3 μm about of yardstick, there is not coiled structure.This phenomenon shows in atmospheric conditions, using urine
Element cannot obtain ldh nanometer roll as alkaline matter, and this proves that pressure and urea need collective effect just can obtain ldh further
Nanometer roll.
Claims (5)
1. a kind of preparation method of layered duplex metal hydroxide nanometer volume is it is characterised in that comprise the steps:
(1) cationic surfactant, cosurfactant and alkanes oil phase are mixed at room temperature, obtain homogeneous
Stable milky suspension system；
Described cationic surfactant is Cetyltrimethylammonium bromide, OTAC, hexadecane
Base trimethylammonium bromide, hexadecyltrimethylammonium chloride, TTAB, tetradecyltrimethylammonium chlorination
Ammonium, DTAB, DTAC, dodecyl benzyl dimethyl ammonium chloride, the tetradecane
Base dimethyl benzyl ammonium chloride, cetalkonium chloride or stearyl dimethyl benzyl ammonium chloride；
Described cosurfactant is n-butanol, n-amyl alcohol, n-hexyl alcohol or n-heptanol；
(2) soluble divalent metal salt and soluble trivalent metal salt are mixed to get salting liquid with deionized water, are added to step
Suddenly, in the milky suspension system that (1) obtains, obtain microemulsion system；
Described alkanes oil phase is 1:0.15～0.5 with the volume ratio of total deionized water；
The molal weight of described surfactant and total deionized water is than for 1:10～36；
Described cosurfactant is 1:0.3～6 with the volume ratio of total deionized water；
Described total deionized water is step (2) and step (3) institute deionized water summation；(3) by alkaline matter and deionization
Water mixes, and is then added in the microemulsion system that step (2) obtains, after continuously stirred 0.5～5h, then through water at 105～120 DEG C
Thermal response 8～20h, obtains described layered duplex metal hydroxide nanometer volume.
2. the preparation method of layered duplex metal hydroxide nanometer according to claim 1 volume is it is characterised in that described
Alkanes oil phase is n-hexane, normal heptane, normal octane or hexamethylene.
3. the preparation method of layered duplex metal hydroxide nanometer according to claim 1 volume is it is characterised in that described
Bivalent metal ion in soluble divalent metal salt is co2+、zn2+、ni2+、mg2+One of or two kinds；
Trivalent metal ion in described soluble trivalent metal salt is al3+、fe3+、cr3+One of or two kinds；
Described soluble divalent metal salt, the anion of soluble trivalent metal salt are cl-、no3 -、so4 2-One of or two
Kind.
4. the preparation method of layered duplex metal hydroxide nanometer according to claim 3 volume is it is characterised in that step
(2), in, in described salting liquid, soluble divalent metal salt and the total concentration of soluble trivalent metal salt are 0.01～1mol/l, can
The molal weight of soluble divalent metal salt and soluble trivalent metal salt than for 0.5～5:1, soluble divalent metal salt and solvable
The molal weight of property trivalent metal salt total amount and alkaline matter is than for 1:1～10.
5. the preparation method of layered duplex metal hydroxide nanometer according to claim 1 volume is it is characterised in that described
Alkaline matter is urea or ammoniacal liquor.
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