CN102205981A - Preparation method of layered compound metal hydroxide for controlling surface defects and surface potentials - Google Patents
Preparation method of layered compound metal hydroxide for controlling surface defects and surface potentials Download PDFInfo
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- CN102205981A CN102205981A CN2011101080245A CN201110108024A CN102205981A CN 102205981 A CN102205981 A CN 102205981A CN 2011101080245 A CN2011101080245 A CN 2011101080245A CN 201110108024 A CN201110108024 A CN 201110108024A CN 102205981 A CN102205981 A CN 102205981A
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- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000007547 defect Effects 0.000 title abstract description 7
- -1 compound metal hydroxide Chemical class 0.000 title abstract 4
- 238000001816 cooling Methods 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- 230000002950 deficient Effects 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 7
- 230000006911 nucleation Effects 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 51
- 239000010410 layer Substances 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of layered compound metal hydroxide for controlling surface defects and surface potentials in the technical field of preparation of inorganic functional materials. By the preparation method, after a crystallization reaction for the layered compound metal hydroxide is finished, the surface defects and the surface electric properties of crystals are simultaneously controlled by different cooling methods, so that the method is easy to operate and realize. Higher cooling rate is achieved, so that more defects are generated on surfaces of layered compound metal hydroxide crystals, electric charges are more non-uniformly distributed on the surfaces of the crystals, and lower Zeta potentials are generated; therefore, catalysis, ultraviolet rejection and flame retarding effects of products are influenced.
Description
Technical field:
The invention belongs to the inorganic functional material preparing technical field, the layered composite metal hydroxides preparation method of particularly a kind of control surface defective and surface potential.
Background technology:
Layered composite metal hydroxides (Layered Double Hydroxides is called for short LDHs) is hydrotalcite again, is a kind of typical anionic type laminated material, and its chemical constitution formula is [M
2+ 1-xM
3+ x(OH)
2] A
N- X/nMH
2O, wherein M
2+, M
3+Represent divalence and trivalent metal cation respectively, A
N-Be interlayer anion, x is M
3+The ionic molar fraction, m is the quantity of crystal water.The kind of the element kind of LDHs main body laminate and proportion of composing, interlayer object and quantity is modulation in relative broad range as required, thereby obtains a series of materials with special construction and performance.The adjustable sex change of LDHs The Nomenclature Composition and Structure of Complexes and the multifunctionality that is caused thus, make it become the type material that a class has research potential and application prospect, be widely used in fields such as fire-retardant, resin treatment, plastic sheeting for farm use as functional agents such as the high smoke-inhibiting flame retardant agent of Halogen, non-toxic heat stabilizer, selective infrared absorbing material and ultraviolet blocking materials.
The surface imperfection of layered composite metal hydroxides and surface potential have significant effects to its performance, as catalytic performance, ultraviolet-resistant performance, flame retardant properties, particle aggregation performance etc.Be that thermograde and concentration gradient during by the control crystallization realizes generally to the plane of crystal defect Control, patent of invention 200610108599.6 provides a kind of defective or strained method in the non-diamond crystal of eliminating under high pressure-temperature, from defect-containing crystal and pressure medium are provided, crystal and pressure medium are placed in the high pressure small vessels, place high-tension apparatus again, handling under sufficiently high pressure pyritous reaction conditions is enough to eliminate one or more defectives or releasing strained time in its single crystal.
And, it is generally acknowledged that identical its surface potential of material of composition is identical to surface electrical behavior, still do not have method the crystalline surface potential with same composition is controlled.When the surface potential of research same composition material, only come the control surface current potential, document (golden will beautiful jade .Mg-Al-NO by adding methods such as ionogen
3The research of layered double hydroxide electrical property. chemical journal .2003,61 (8): 1208-1212.) adopt electrophoretic method to determine Mg-Al-NO in different ionogen (LiCl, NaCl and the KCl) solution with potentiometric titration
3Electrochemistry physical quantitys such as layered double hydroxide particulate zeta-potential, iso-electric point, permanent charge density and point of zero electric charge have been inquired into ionogen, pH value and sample chemical and have been formed Mg-Al-NO
3The influence of LDH electrical property.Discover monovalent cation Li
+, Na
+, K
+To Mg-Al-NO
3LDH particulate iso-electric point is influential, and iso-electric point is reduced successively; Because the existence of permanent charge, iso-electric point and point of zero electric charge are inconsistent.Along with the increase of Al content in the sample, permanent charge density increases successively, and point of zero electric charge increases successively, and iso-electric point reduces successively.
Summary of the invention:
The preparation method who the purpose of this invention is to provide the layered composite metal hydroxides of a kind of control surface defective and surface potential.
Concrete operations step of the present invention is as follows:
A. be Mg in molar ratio with solvable divalent metal magnesium salts and solvable trivalent metal aluminium salt
2+/ Al
3+=2～4 are dissolved in and are made into mixing salt solution, wherein [Mg in the deionized water
2+]=0.8～1.6mol/L, the negatively charged ion of magnesium salts and aluminium salt is a sulfate radical; Press n (NaOH)/[n (Mg
2+)+n (Al
3+)]=1.6～2.5 and [NaCO
3]=2[Al
3+] molar ratio, with NaOH and Na
2CO
3Be dissolved in the mixed ammonium/alkali solutions that is made into equal volume in the deionized water; Above-mentioned two solution are injected fast nucleation of rotation liquid film reactor with volume pump simultaneously with the equal volume flow,, obtain the layered composite metal hydroxides slurries the slurries that obtain 100 ℃ of backflow crystallization 0.5～6.0 hour in there-necked flask;
B. to the slurries after the crystallization adopt fast cooling or at a slow speed temperature reduction way cool off, treat to carry out when temperature drops to room temperature centrifuge washing and to neutrality, obtain the layered composite metal hydroxides filter cake; Drying is 1～10 hour under 50～180 ℃, obtains the layered composite metal hydroxides powder.
The chemical general formula of described layered composite metal hydroxides is:
[Mg
2+ 1-xAl
3+ x(OH)
2]
x+(CO
3 n-)
x/2·mH
2O，
Wherein x is Al
3+/ (Mg
2++ Al
3+) mol ratio, span is 0.2≤x≤0.33, m is the quantity of crystal water, its span is 0≤m≤2.
Described fast cooling i.e. 0.1～1h drops to 20 ℃ from 100 ℃.
Described fast cooling adopts cryogenic thermostat reactive bath technique, ice-water bath, the bath of different types of cryosel, cooled with liquid nitrogen; The ratio of reactive bath technique employing deionized water and ethylene glycol volume is 1: 3 a mixing solutions, the temperature of reactive bath technique is set between 0～-40 ℃, and the low more then rate of temperature fall of design temperature is fast more, when temperature is set at-30 ℃, the flask that slurries are housed is placed reactive bath technique, and 0.3h drops to 20 ℃ from 100 ℃.
Described cooling at a slow speed i.e. 6～24h drops to 20 ℃ from 100 ℃.
The mode of the described employing of cooling at a slow speed temperature programmed control is lowered the temperature and is promptly progressively cooled off with the baking oven or the water bath with thermostatic control of a conventional oven, tape program temperature control.
The lattice fringe long-range order distance of the layered composite metal hydroxides that obtains of cooling is 13～27nm at a slow speed, and Zeta potential is 18～24mv; The lattice fringe long-range order distance that fast cooling obtains layered composite metal hydroxides is 2～18nm, and Zeta potential is 13～18mv.
The invention has the beneficial effects as follows and adopt different cool-down methods that the plane of crystal defective and the surface electrical behavior of layered composite metal hydroxides are controlled simultaneously, simple to operate being easy to realized.The layered composite metal hydroxides plane of crystal defective that rate of temperature fall obtains more soon is many more, and electric charge distributes inhomogeneous more at plane of crystal, and Zeta (ζ) current potential is low more, and then catalysis, ultraviolet-resistant, the fire retardation of product exerted an influence.
Description of drawings
Fig. 1 is the XRD spectra of the layered composite metal hydroxides that two kinds of different cooling methods of employing obtain among the embodiment 1; (a) being the product of fast cooling, (b) is the product of lowering the temperature at a slow speed.
Fig. 2 is the high-resolution-ration transmission electric-lens photo of the layered composite metal hydroxides that two kinds of different cooling methods of employing obtain among the embodiment 1; A is the product of fast cooling, and b is the product of lowering the temperature at a slow speed.
Embodiment
Layered composite metal hydroxides surface imperfection and surface potential controlling party ratio juris are: the inorganic particulate surface generally all has the electric charge of different densities, has surface potential, the electric charge of its surface meeting absorption contrary sign constitutes electrostatic double layer in solution, and wherein the gegenion adsorbed close layer that mortise forms on the surface owing to strong attraction is called Stern (stern) layer.The electric charge of these contrary signs concentration from the near to the remote reduces gradually, and the voltage that produces at electrostatic double layer slipping plane place is called Zeta (ζ) current potential, and its numerical value can calculate by the mensuration of electrophoresis or electric osmose speed.
MgAl-CO
3-LDHs similar is in Mg (OH)
2, be by MgO
6Octahedra shared prismatic becomes unit layer, is positioned at the Mg on the layer
2+Can be by the Al of similar radius in certain scope
3+Isomorphous substitution makes Mg, Al, OH sheath positively charged, and these positive charges are positioned at the CO of interlayer
3 2-Neutralization.The theoretical veneer structure of LDHs is that divalence and trivalent ion are evenly arranged on laminate, trivalent ion as far as possible mutually away from, make laminate electric charge uniform distribution, this moment, energy was minimum.
When the LDHs crystal is lowered the temperature at a slow speed, Mg
2+And Al
3+On laminate, there is the competent time to rearrange, can on laminate, reaches uniform distribution, near ideal crystal structure, Mg
2+, Al
3+There is not clustering phenomena, laminate electric charge uniform distribution, the gegenion of grain surface absorption this moment is (as OH
-, CO
3 2-Deng) forming concentration and the equally distributed Stern layer of thickness on the surface, the Stern layer is also identical everywhere at particle surface with Zeta (ζ) current potential that the slipping plane place of bulk solution produces.When the LDHs crystal is carried out fast cooling, Mg on the laminate
2+And Al
3+Distribution when keeping nucleation does not have adequate time to rearrange, and can not reach uniform distribution, departs from the ideal crystal structure, makes Mg
2+, Al
3+Produce and assemble, form point defect on the surface; Laminate electric density is local to be increased, and this zone is strengthened the gegenion adsorptive power in the solution, and then makes the gegenion of surface adsorption present the multilayer arrangement, causes the stern layer to thicken, and slipping plane moves outward, thereby surface potential is descended rapidly.
Embodiment 1:
With 43.34g MgSO
4With 59.98g Al
2(SO
4)
318H
2O is dissolved in and is made into the 300ml mixing salt solution in the deionized water, with 34.56g NaOH and 38.16g Na
2CO
3Be dissolved in and be made into the 300ml alkaline solution in the deionized water, two kinds of solution are injected rotation liquid film reactor nucleation fast with volume pump simultaneously with the equal volume flow, the slurries that obtain are divided into two parts by identical quality, place the following 100 ℃ of backflow 0.5h of there-necked flask agitation condition of two 500ml to obtain the layered composite metal hydroxides slurries respectively;
One of them there-necked flask is placed the cryogenic thermostat reactive bath technique, and the ratio of reactive bath technique employing deionized water and ethylene glycol volume is 1: 3 a mixing solutions, and the low-temp reaction bath temperature is set at-30 ℃, and 0.3h rear slurry temperature can be reduced to 20 ℃; Slurries in another there-necked flask are set at slowly cooling in 20 ℃ the thermostat container in temperature, and temperature can be reduced to 20 ℃ behind the 6h;
The slurries centrifuge washing that two kinds of different cooling methods are obtained is to neutral, and will wash the product of getting well and place 70 ℃ the dry 9h of baking oven, obtains the complex metal hydroxide powder.
The chemical formula of the complex metal hydroxide of preparation is: [Mg
2+ 1-xAl
3+ x(OH)
2]
X+(CO
3 N-)
X/2MH
2O, x=0.33 wherein, m=1.2.
(Cu target K alpha-ray, 5 ° of sweep velocitys/min), result as shown in Figure 1, a is the product of fast cooling, and b is the product of cooling at a slow speed to adopt the Japanese Shimadzu XRD-6000 of company type X-ray powder diffraction instrument to measure the crystalline structure of above-mentioned sample.As can be seen from the figure, the LDHs that obtains of cooling (003), (006) diffraction peak are strong and peak width at half height is less at a slow speed.Can calculate crystalline relative crystallinity data from the XRD data, the relative crystallinity method of calculation adopt the Crystallinity option in the Shimadzu XRD-6000 type X-ray powder diffraction instrument V4.1 of the function software version to calculate.The relative crystallinity of fast cooling product is 32.42%, and the relative crystallinity of the product of lowering the temperature at a slow speed is 34.98%, the crystalline structure that the product of lowering the temperature at a slow speed is described the complete of product of faster lowering the temperature.
The JEM-2100 type high resolution transmission electron microscopy (HRSEM) that adopts Japanese JEOL company characterizes the lattice fringe of sample.The result as shown in Figure 2, a is the product of fast cooling, b be at a slow speed the cooling product.From the HRTEM photo as can be seen, the lattice fringe of fast cooling LDHs is disorderly, towards a plurality of direction orientations, length to the unidirectional lattice fringe continuity of sample is measured, the distance that obtains its long-range order is 2.09～8.57nm, crystal long-range order degree is lower, regularity is relatively poor, the atom of this explanation on crystal face as yet not formation rule arrange, especially raise the atom that there are a large amount of lack of alignment in boundary at crystalline substance.The lattice fringe differently-oriented directivity number of sample of lowering the temperature at a slow speed reduces, and the crystal regularity strengthens, and the atom in this explanation crystal levels off to regularly arranged, and the distance of its long-range order is 15.54～17.35nm, and the long-range order degree obviously increases.
With the abundant ultra-sonic dispersion of complex metal hydroxide powder in deionized water, accurately be mixed with the water-sol of 1.0g/L, leave standstill 24h behind the ultra-sonic dispersion, after treating system balancing, adopt the Zeta potential of the Zetasizer Nano ZS90 type particle-size analyzer working sample of Britain Ma Erwen company, adopt the pH value of the laboratory pH meter working sample of Mettler Toledo Inc..The Zeta potential of fast cooling product is 13.6mv, and the Zeta potential of the product of lowering the temperature at a slow speed is 19.2mv, and the pH value of two kinds of products is 8.85, illustrates that the product surface of cooling has more positive charge at a slow speed.
Embodiment 2:
With 43.34g MgSO
4With 39.98g Al
2(SO
4)
318H
2O is dissolved in and is made into the 300ml mixing salt solution in the deionized water, with 30.72g NaOH and 25.44g Na
2CO
3Be dissolved in and be made into the 300ml alkaline solution in the deionized water, two kinds of solution are injected rotation liquid film reactor nucleation fast with volume pump simultaneously with the equal volume flow, the slurries that obtain are divided into two parts by identical quality, place the following 100 ℃ of backflow 1.0h of there-necked flask agitation condition of two 500ml to obtain the layered composite metal hydroxides slurries respectively;
Place the frozen water water-bath that is equipped with 0 ℃ to cool off one of them there-necked flask, 1h rear slurry temperature can be reduced to 20 ℃; Slurries in another there-necked flask cool off in the baking oven of tape program temperature control, and setting rate of temperature fall is 0.1 ℃/min, and 13.3h rear slurry temperature can be reduced to 20 ℃;
The slurries centrifuge washing that two kinds of different cooling methods are obtained is to neutral, and will wash the product of getting well and place 110 ℃ the dry 6h of baking oven, obtains the complex metal hydroxide powder.
The chemical formula of the complex metal hydroxide of preparation is: [Mg
2+ 1-xAl
3+ x(OH)
2]
X+(CO
3 N-)
X/2MH
2O, x=0.25 wherein, m=1.1.
Adopt the Crystallinity option in the Shimadzu XRD-6000 type X-ray powder diffraction instrument V4.1 of the function software version to calculate the crystalline relative crystallinity.The relative crystallinity of fast cooling product is 30.98%, and the relative crystallinity of the product of lowering the temperature at a slow speed is 32.51%, the crystalline structure that the product of lowering the temperature at a slow speed is described the complete of product of faster lowering the temperature.
The JEM-2100 type high resolution transmission electron microscopy that adopts Japanese JEOL company characterizes the lattice fringe of sample.The lattice fringe long-range order distance of fast cooling product is 5.73～11.82nm, and the long-range order distance of the product of lowering the temperature at a slow speed is 16.33～21.56nm, and the long-range order degree of the product of lowering the temperature at a slow speed is higher.
With the preparation the abundant ultra-sonic dispersion of complex metal hydroxide powder in deionized water, accurately be mixed with the water-sol of 1.0g/L, leave standstill 24h behind the ultra-sonic dispersion, after treating system balancing, adopt the Zeta potential of the Zetasizer NanoZS90 type particle-size analyzer working sample of Britain Ma Erwen company, adopt the pH value of the laboratory pH meter working sample of Mettler Toledo Inc..The Zeta potential of fast cooling product is 17.9mv, and the Zeta potential of the product of lowering the temperature at a slow speed is 20.6mv, and the pH value of two kinds of products is 8.99.
Embodiment 3:
With 43.34g MgSO
4With 29.99g Al
2(SO
4)
318H
2O is dissolved in and is made into the 300ml mixing salt solution in the deionized water, with 28.80g NaOH and 19.08g Na
2CO
3Be dissolved in and be made into the 300ml alkaline solution in the deionized water, two kinds of solution are injected rotation liquid film reactor nucleation fast with volume pump simultaneously with the equal volume flow, the slurries that obtain are divided into two parts by identical quality, place the following 100 ℃ of backflow 2.0h of there-necked flask agitation condition of two 500ml to obtain the layered composite metal hydroxides slurries respectively;
One of them there-necked flask is placed the cryogenic thermostat reactive bath technique, and the ratio of reactive bath technique employing deionized water and ethylene glycol volume is 1: 3 a mixing solutions, and the low-temp reaction bath temperature is set at-20 ℃, and 0.5h rear slurry temperature can be reduced to 20 ℃; Slurries in another there-necked flask are slowly cooling in 20 ℃ of water-baths, and temperature can be reduced to 20 ℃ behind the 8h;
The slurries centrifuge washing that two kinds of different cooling methods are obtained is to neutral, and will wash the product of getting well and place 130 ℃ the dry 3h of baking oven, obtains the complex metal hydroxide powder.
The chemical formula of the complex metal hydroxide of preparation is: [Mg
2+ 1-xAl
3+ x(OH)
2]
X+(CO
3 N-)
X/2MH
2O, x=0.2 wherein, m=1.4.
Adopt the Crystallinity option in the Shimadzu XRD-6000 type X-ray powder diffraction instrument V4.1 of the function software version to calculate the crystalline relative crystallinity.The relative crystallinity of fast cooling product is 22.48%, and the relative crystallinity of the product of lowering the temperature at a slow speed is 25.12%, the crystalline structure that the product of lowering the temperature at a slow speed is described the complete of product of faster lowering the temperature.
The JEM-2100 type high resolution transmission electron microscopy that adopts Japanese JEOL company characterizes the lattice fringe of sample.The lattice fringe long-range order distance of fast cooling product is 3.87～8.75nm, and the long-range order distance of the product of lowering the temperature at a slow speed is 13.64～17.52nm, and the long-range order degree of the product of lowering the temperature at a slow speed is higher.
With the abundant ultra-sonic dispersion of complex metal hydroxide powder in deionized water, accurately be mixed with the water-sol of 1.0g/L, leave standstill 24h behind the ultra-sonic dispersion, after treating system balancing, adopt the Zeta potential of the Zetasizer Nano ZS90 type particle-size analyzer working sample of Britain Ma Erwen company, adopt the pH value of the laboratory pH meter working sample of Mettler Toledo Inc..The Zeta potential of fast cooling product is 13.9mv, and the Zeta potential of the product of lowering the temperature at a slow speed is 18.3mv, and the pH value of two kinds of products is 9.50.
Embodiment 4:
With 28.89g MgSO
4With 39.98g Al
2(SO
4)
318H
2O is dissolved in and is made into the 300ml mixing salt solution in the deionized water, with 23.04g NaOH and 25.44g Na
2CO
3Be dissolved in and be made into the 300ml alkaline solution in the deionized water, two kinds of solution are injected rotation liquid film reactor nucleation fast with volume pump simultaneously with the equal volume flow, the slurries that obtain are divided into two parts by identical quality, place the following 100 ℃ of backflow 4.0h of there-necked flask agitation condition of two 500ml to obtain the complex metal hydroxide slurries respectively;
Place the water-bath that-10 ℃ of cryosels are housed to cool off one of them there-necked flask, 0.8h rear slurry temperature can be reduced to 20 ℃; Slurries in another there-necked flask are progressively cooling in the thermostat container of tape program temperature control, and setting rate of temperature fall is 0.06 ℃/min, and 22.2h rear slurry temperature can be reduced to 20 ℃;
The slurries centrifuge washing that two kinds of different cooling methods are obtained is to neutral, and will wash the product of getting well and place 160 ℃ the dry 2h of baking oven, obtains the complex metal hydroxide powder.
The chemical formula of the complex metal hydroxide of preparation is: [Mg
2+ 1-xAl
3+ x(OH)
2]
X+(CO
3 N-)
X/2MH
2O, x=0.33 wherein, m=0.8.
Adopt the Crystallinity option in the Shimadzu XRD-6000 type X-ray powder diffraction instrument V4.1 of the function software version to calculate the crystalline relative crystallinity.The relative crystallinity of fast cooling product is 39.41%, and the relative crystallinity of the product of lowering the temperature at a slow speed is 40.77%, the crystalline structure that the product of lowering the temperature at a slow speed is described the complete of product of faster lowering the temperature.
The JEM-2100 type high resolution transmission electron microscopy that adopts Japanese JEOL company characterizes the lattice fringe of sample.The lattice fringe long-range order distance of fast cooling product is 7.49～17.23nm, and the long-range order distance of the product of lowering the temperature at a slow speed is 20.65～26.74nm, and the long-range order degree of the product of lowering the temperature at a slow speed is higher.
With the abundant ultra-sonic dispersion of complex metal hydroxide powder in deionized water, accurately be mixed with the water-sol of 1.0g/L, leave standstill 24h behind the ultra-sonic dispersion, after treating the dispersion system balance, adopt the Zeta potential of the Zetasizer NanoZS90 type particle-size analyzer working sample of Britain Ma Erwen company, adopt the pH value of the laboratory pH meter working sample of Mettler Toledo Inc..The Zeta potential of fast cooling product is 17.5mv, and the Zeta potential of the product of lowering the temperature at a slow speed is 23.6mv, and the pH value of two kinds of products is 8.57.
Claims (7)
1. the layered composite metal hydroxides preparation method of control surface defective and surface potential is characterized in that its concrete operations step is as follows:
A. be Mg in molar ratio with solvable divalent metal magnesium salts and solvable trivalent metal aluminium salt
2+/ Al
3+=2～4 are dissolved in and are made into mixing salt solution, wherein [Mg in the deionized water
2+]=0.8～1.6mol/L, the negatively charged ion of magnesium salts and aluminium salt is a sulfate radical; Press n (NaOH)/[n (Mg
2+)+n (Al
3+)]=1.6～2.5 and [NaCO
3]=2[Al
3+] molar ratio, with NaOH and Na
2CO
3Be dissolved in the mixed ammonium/alkali solutions that is made into equal volume in the deionized water; Above-mentioned two solution are injected fast nucleation of rotation liquid film reactor with volume pump simultaneously with the equal volume flow,, obtain the layered composite metal hydroxides slurries the slurries that obtain 100 ℃ of backflow crystallization 0.5～6.0 hour in there-necked flask;
B. to the slurries after the crystallization adopt fast cooling or at a slow speed temperature reduction way cool off, treat to carry out when temperature drops to room temperature centrifuge washing and to neutrality, obtain the layered composite metal hydroxides filter cake; Drying is 1～10 hour under 50～180 ℃, obtains the layered composite metal hydroxides powder.
2. the layered composite metal hydroxides preparation method of a kind of control surface defective according to claim 1 and surface potential is characterized in that the chemical general formula of described layered composite metal hydroxides is:
[Mg
2+ 1-xAl
3+ x(OH)
2]
x+(CO
3 n-)
x/2·mH
2O，
Wherein x is Al
3+/ (Mg
2++ Al
3+) mol ratio, span is 0.2≤x≤0.33, m is the quantity of crystal water, its span is 0≤m≤2.
3. the layered composite metal hydroxides preparation method of a kind of control surface defective according to claim 1 and surface potential is characterized in that, described fast cooling i.e. 0.1～1h drops to 20 ℃ from 100 ℃.
4. according to the layered composite metal hydroxides preparation method of arbitrary described a kind of control surface defective of claim 1-3 and surface potential, it is characterized in that described fast cooling adopts cryogenic thermostat reactive bath technique, ice-water bath, the bath of different types of cryosel, cooled with liquid nitrogen; The ratio of reactive bath technique employing deionized water and ethylene glycol volume is 1: 3 a mixing solutions, the temperature of reactive bath technique is set between 0～-40 ℃, and the low more then rate of temperature fall of design temperature is fast more, when temperature is set at-30 ℃, the flask that slurries are housed is placed reactive bath technique, and 0.3h drops to 20 ℃ from 100 ℃.
5. the layered composite metal hydroxides preparation method of a kind of control surface defective according to claim 1 and surface potential is characterized in that, described cooling at a slow speed i.e. 6～24h drops to 20 ℃ from 100 ℃.
6. according to the layered composite metal hydroxides preparation method of claim 1,2 or 5 described a kind of control surface defectives and surface potential, it is characterized in that the mode of the described employing of cooling at a slow speed temperature programmed control is lowered the temperature and promptly progressively cooled off with the baking oven or the water bath with thermostatic control of a conventional oven, tape program temperature control.
7. according to the layered composite metal hydroxides preparation method of claim 1,2,3 or 5 arbitrary described a kind of control surface defectives and surface potential, it is characterized in that, the lattice fringe long-range order distance of the layered composite metal hydroxides that obtains of cooling is 13～27nm at a slow speed, and Zeta potential is 18～24mv; The lattice fringe long-range order distance that fast cooling obtains layered composite metal hydroxides is 2～18nm, and Zeta potential is 13～18mv.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103723748A (en) * | 2013-12-30 | 2014-04-16 | 北京化工大学 | Method for preparing ultraviolet barrier material by taking hydrotalcite as precursor |
| CN104558775A (en) * | 2015-01-12 | 2015-04-29 | 北京化工大学 | Hydrotalcite acid acceptor for polyolefin |
| CN114976064A (en) * | 2022-05-24 | 2022-08-30 | 合肥工业大学 | Preparation method of high-stability non-noble metal catalyst for alkaline anionic membrane fuel cell |
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| CN1288078A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Method for synthesis of well-dispersed and super fine anion laminated material |
| CN1358691A (en) * | 2000-12-14 | 2002-07-17 | 北京化工大学 | All return mixing-liquid film reactor and use in prepairng ultrafine anion layer shape material |
| CN101503182A (en) * | 2009-03-27 | 2009-08-12 | 北京化工大学 | Method for in situ modification by isoelectric point layered composite metal hydroxides |
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|---|---|---|---|---|
| CN1288078A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Method for synthesis of well-dispersed and super fine anion laminated material |
| CN1358691A (en) * | 2000-12-14 | 2002-07-17 | 北京化工大学 | All return mixing-liquid film reactor and use in prepairng ultrafine anion layer shape material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103723748A (en) * | 2013-12-30 | 2014-04-16 | 北京化工大学 | Method for preparing ultraviolet barrier material by taking hydrotalcite as precursor |
| CN103723748B (en) * | 2013-12-30 | 2015-07-08 | 北京化工大学 | Method for preparing ultraviolet barrier material by taking hydrotalcite as precursor |
| CN104558775A (en) * | 2015-01-12 | 2015-04-29 | 北京化工大学 | Hydrotalcite acid acceptor for polyolefin |
| CN114976064A (en) * | 2022-05-24 | 2022-08-30 | 合肥工业大学 | Preparation method of high-stability non-noble metal catalyst for alkaline anionic membrane fuel cell |
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