CN102659081A - Layered double hydroxides (LDHs) loading highly-dispersed fullerenes and preparing method of LDHs - Google Patents
Layered double hydroxides (LDHs) loading highly-dispersed fullerenes and preparing method of LDHs Download PDFInfo
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- CN102659081A CN102659081A CN2012101265157A CN201210126515A CN102659081A CN 102659081 A CN102659081 A CN 102659081A CN 2012101265157 A CN2012101265157 A CN 2012101265157A CN 201210126515 A CN201210126515 A CN 201210126515A CN 102659081 A CN102659081 A CN 102659081A
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- naphthylacetic acid
- soccerballene
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Abstract
The invention belongs to the field of organic-inorganic composite materials and relates to layered double hydroxides (LDHs) loading highly-dispersed fullerenes and a preparing method of the LDHs. The method of the LDHs includes the steps of firstly preparing precursors of the LDHs, then preparing naphthylacetic acid intercalated LDHs, forming a hydrophobic environment containing a plurality of naphthalene groups in layers of naphthylacetic acid intercalated LDHs, and finally fixing the fullerenes into the layers of the LDHs. According to the LDHs loading the highly-dispersed fullerenes and the preparing method of the LDHs, the fullerene and naphthylacetic acid intercalated LDHs are of supramolecular structures, crystal structures of the LDHs are the crystal structures of layered double hydroxide-like materials, and the chemical formula is [ (M2+)1-x(M3+)x(OH)2 ]x+(NAA-)x(C60)y-water(1/m), wherein x=0.25-0.33,y=0.05-0.1, m=3-6, the m relates to the number of crystal water molecules in the layers, M2+ relates to a divalent metal ion, and M3+relates to a trivalent metal ion of Al3+. According to the LDHs loading the highly-dispersed fullerenes and the preparing method of the LDHs, due to high interaction forces between the fullerenes (C60) and the naphthylacetic acid, the prepared fullerene and naphthylacetic acid intercalated LDHs have stable intercalation structures and can be used for preparing non-linear optics materials, strong magnetic materials and the like, and the preparing method is simple, practicable and easy to operate.
Description
Technical field
The invention belongs to the composite organic-inorganic material field, relate to hydrotalcite material of a kind of load high dispersion fullerene and preparation method thereof.
Background technology
Hydrotalcite (Layered Double Hydroxides is called for short LDHs) is an anionoid type stratified material, and its chemical constitution is [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/nMH
2O.This material is made up of the laminate that is parallel to each other, and laminate has permanent positive charge.M
2+, M
3+Be divalence and trivalent metal cation, interlayer has tradable negatively charged ion A
N-To keep charge balance.There is the strong covalent bond effect in element between the hydrotalcite laminate, and interlayer anion links to each other with ionic linkage with laminate, and whole crystal is electroneutral.Because of the laminate structure of hydrotalcite uniqueness and the interchangeability of interlayer anion, introduce functional negatively charged ion to hydrotalcite layers, can prepare the intercalation material of difference in functionality, be widely used in fields such as catalysis, absorption, IX.
Soccerballene (C
60) be a kind of molecule that constitutes by 60 carbon atoms, because its likeness in form football has another name called football alkene.C
60Be the stable molecule that is formed by the carbon atom combination merely, it has 60 summits and 32 faces, and wherein 12 is regular pentagon, and 20 is regular hexagon.Its relative molecular mass is about 720.At C
60In the molecule, each carbon atom overlaps each other with a p track and forms a closedshell electronic structure that contains 60 πDian Zis, therefore in the cage of almost spherical with cage outside all round the πDian Zi cloud.Molecular Orbital Calculation shows that soccerballene has bigger delocalized energy.The present C that discovers
60Many excellent properties are arranged, like superconduction, ferromagnetism, high pressure resistant, resist chemical etc.Science personnel further adopt special technique with C
60Molecular dispersion ground is fixed in solid surface or interlayer, finds that these materials have and C
60The character that crystal is different.
At document (1) J.Am.Chem.Soc., 1996, among the 118:4411-4418, people such as Soofin Cheng are at first with C
60Intercalation is gone in the hydrotalcite of dodecyl sulphate root modification, and has detected the characteristic of the aspects such as crystalline structure, thermogravimetric, ir spectra and nuclear-magnetism of this matrix material.Discover C with free state
60Compare, get into the C of hydrotalcite layers
60Spectrum and nuclear magnetic spectrogram notable difference has all been arranged, they propose this is owing to get into C behind the two-dimentional confinement space
60Due to motion is obviously limited.
At document (2) J.Am.Chem.Soc.; 2004; Among the 126:8561-8568; People such as Dimitrios Gournis go into the interlayer of polynite with cation modified soccerballene intercalation, have further analyzed the character of the aspects such as crystalline structure, thermogravimetric, ir spectra and electricity of this material, find that this material has very unique character aspect electricity.
Present domestic document and the patent report that relevant soccerballene is fixed in the hydrotalcite layers of naphthylacetic acid intercalation that still do not have.
Summary of the invention
The object of the invention is hydrotalcite material that provides a kind of load high dispersion fullerene and preparation method thereof, the hydrotalcite material of soccerballene of preparing and naphthylacetic acid intercalation, C
60Strong with the interaction force of naphthylacetic acid, intercalation configuration is stable.
The hydrotalcite material of load high dispersion fullerene of the present invention; Be to prepare the hydrotalcite precursor earlier,, form the hydrophobic environment that contains a large amount of naphthylene groups at interlayer again with naphthylacetic acid root intercalated houghite; Then soccerballene is fixed in hydrotalcite layers; The hydrotalcite of soccerballene of the present invention and naphthylacetic acid intercalation is a supramolecular structure, and its crystalline structure is the crystalline structure of houghite material, and its chemical formula is:
[(M
2+)
1-x(M
3+)
x(OH)
2]
x+(NAA
-)
x(C60)
y·mH
2O
X=0.25～0.33 wherein, y=0.05～0.1, m=3～6, m is the quantity of interlayer crystal water molecule, M
2+Be divalent-metal ion, M
3+Be trivalent metal ion Al
3+
Said M
2+Be Mg
2+, Ni
2+, Zn
2+Or Co
2+, preferred Zn
2+Or Ni
2+
The preparation method of the hydrotalcite material of described load high dispersion fullerene comprises the steps:
The preparation of A, hydrotalcite precursor:
The preparation interlayer anion is NO
3 -Perhaps Cl
-, laminate divalence, Tricationic mol ratio M
2+/ M
3+=2～3 hydrotalcite precursor NO
3-LDHs or Cl-LDHs;
Specifically be with M
2+Soluble salt and Al
3+Soluble salt be mixed with mixing solutions, M wherein
2+/ Al
3+Mol ratio is 2～3, M
2+Volumetric molar concentration be 0.1～1.OM, Al
3+Volumetric molar concentration be 0.05～0.5M; With NaOH is alkaline solution, and wherein the NaOH volumetric molar concentration is 1.0～5.OM, at room temperature N
2Under the protective condition; Adopt two methods of dripping that salts solution and alkaline solution are added in the four-hole bottle; Using 0.1～5.0M NaOH solution adjust pH again after adding is accomplished is 6～10; With 60～90 ℃ of crystallization 12～72h of gained slurries, product is put into whizzer centrifugal 3～5min under rotating speed 2500～3500 commentaries on classics/min, spends CO again
2Water washing is to neutral; Take out 50～90 ℃ of down dry 20～48h of sample, obtain the hydrotalcite precursor;
Described M
2+Soluble salt be hydrochloride or nitrate salt, Al
3+Soluble salt be hydrochloride or nitrate salt, and M
2+Soluble salt and Al
3+The kind of soluble salt identical;
B, naphthylacetic acid root intercalated houghite:
Nafusaku is dissolved in removes CO
2Deionized water in, the hydrotalcite precursor that again steps A is obtained joins in this solution, N
2Protection is heated to 50～70 ℃, stirs reaction 12～48h down, and product is put into whizzer centrifugal 3～5min under rotating speed 2500～3500 commentaries on classics/min, spends CO again
2Water washing is to neutral, and 50～90 ℃ of down dry 20～48h can obtain naphthylacetic acid intercalated houghite NNA-LDHs;
C, soccerballene are fixed in hydrotalcite layers:
The soccerballene crystal is dissolved in the YLENE, adds the naphthylacetic acid intercalated houghite that step B obtains, at N
2Protection is also stirred down; In 50～70 ℃ of altogether hot down 12～48h; Product is used the YLENE thorough washing, puts into whizzer centrifugal 3～5min under rotating speed 2500～3500 commentaries on classics/min, behind 50～90 ℃ of down dry 20～48h, can obtain the hydrotalcite C of soccerballene and naphthylacetic acid intercalation
60/ NNA-LDHs.
The intercalation product that makes is carried out XRD, UV-vis sign, and study its optical property.
Above-mentioned materials is carried out XRD, UV-vis to be characterized and shows the hydrotalcite that has successfully prepared soccerballene and naphthylacetic acid intercalation.Can know that by the XRD structural parameter naphthylacetic acid takes the monolayer alignment mode of axis normal laminate, C in hydrotalcite layers
60After getting into interlayer, interlamellar spacing further increases.And its unit cell parameters a value is close with other hydrotalcite, shows that product has complete laminate structure.From uv-vis spectra, can find out C
60After getting into hydrotalcite layers, occurred and C
60The absorption peak that crystal is similar.
The present invention utilizes the controlled and veneer structure orientation effect of interlayer ion interchangeability, the laminate of hydrotalcite, and the first intercalation of naphthylacetic acid root negatively charged ion (NAA) is got into hydrotalcite layers, makes organic-inorganic nanocomposite.The hydrophobic environment that utilizes naphthylacetic acid to form in hydrotalcite layers again is with soccerballene (C
60) introduce the hydrotalcite layers of naphthylacetic acid intercalation, make the stratified composite that contains high dispersion fullerene.Because naphthalene also has big delocalized pi-bond, with C
60Character is approaching, in the soccerballene that therefore prepares and the hydrotalcite material of naphthylacetic acid intercalation, and C
60Strong with the interaction force of naphthylacetic acid, intercalation configuration is stable.
The present invention has following beneficial effect:
The hydrophobic environment that is rich in delocalized pi-bond that the present invention utilizes the hydrotalcite layers naphthylacetic acid to provide; Can the soccerballene with unique physico-chemical property be assembled into hydrotalcite layers; Realize the immobilization and the enhancement of dispersion of soccerballene, the hydrotalcite material of soccerballene of preparing and naphthylacetic acid intercalation, C
60Strong with the interaction force of naphthylacetic acid, intercalation configuration is stable; Simultaneously can also be through changing the hydrotalcite material that hydrotalcite laminate divalence trivalent metal ion kind prepares a series of soccerballenes and naphthylacetic acid intercalation; This material can be used for preparing nonlinear optical material, strong magnetic material etc.; Its preparation method is simple, is easy to realize.
Description of drawings
Fig. 1 is the structural representation of soccerballene and naphthylacetic acid intercalated houghite;
Fig. 2 is the soccerballene of embodiment 1 preparation and the X-ray powder diffraction figure of naphthylacetic acid intercalated houghite;
Among Fig. 2:
A-hydrotalcite precursor;
B-naphthylacetic acid intercalated houghite;
C-soccerballene and naphthylacetic acid intercalated houghite;
Fig. 3 is the soccerballene of embodiment 1 preparation and the ultraviolet-visible spectrogram of naphthylacetic acid intercalated houghite;
Among Fig. 3:
The a-soccerballene;
B-naphthylacetic acid intercalated houghite;
C-soccerballene and naphthylacetic acid intercalated houghite.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Steps A: take by weighing 17.8g Zn (NO
3)
26H
2O, 11.3g Al (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Water preparation mixing salt solution, other gets 5.6g NaOH and is dissolved in 50ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2Protection adopts two methods of dripping that salts solution and alkaline solution are added in the four-hole bottle violent stirring.Using 0.1mol/LNaOH solution to regulate the pH value is 7.The gained slurries are in 60 ℃ of crystallization 72h, and product is put into whizzer centrifugal 5min under rotating speed 2500 commentaries on classics/min, spends CO again
2Water washing is to neutral; Take out sample and characterize behind the dry 48h down for 50 ℃, obtain ZnAl-NO
3-LDHs, its Zn
2+/ Al
3+=2.
Step B: with the sodium salt [C of 10.9g naphthylacetic acid
12H
9O
2Na] solid is dissolved in 100mL and removes CO
2Deionized water after change in the four-hole bottle, add again and fill 20g hydrotalcite precursor ZnAl-NO
3-LDHs, N
2Protection is heated to 50 ℃, stirs reaction 48h down.Product is put into whizzer centrifugal 5min under rotating speed 2500 commentaries on classics/min, spends CO again
2Water washing is to neutral, and 50 ℃ of following dry 48h can obtain naphthylacetic acid intercalated houghite ZnAl-NAA-LDHs.
Step C: with 0.1gC
60Be dissolved in the 100mL YLENE, add in the four-hole bottle, add the 10g of naphthylacetic acid intercalated houghite described in the step B again, at N
2Protect and also stir down, 50 ℃ are total to hot 48h down, and product is used the YLENE thorough washing, puts into whizzer centrifugal 5min under rotating speed 2500 commentaries on classics/min, behind dry 48h under 50 ℃, can obtain the hydrotalcite ZnAl-C of soccerballene and naphthylacetic acid intercalation
60/ NNA-LDHs.
In the present embodiment, the product chemical formula is: [(Zn
2+)
0.67(Al
3+)
0.33(OH)
2]
0.33+(NAA
-)
0.33(C
60)
0.053H
2O.Can be known that by X-ray diffractogram hydrotalcite has comparatively ideal six side's laminate structures, crystalline phase is single, and percent crystallinity is better.The d of naphthylacetic acid intercalated houghite (ZnAl-NAA-LDHs)
003Interlamellar spacing is 1.94nm, than intercalation precursor ZnAl-NO
3The interlamellar spacing of-LDHs increases 1.05nm.This laminate expansion phenomenon shows that naphthylacetic acid successfully inserts the LDHs interlayer.After soccerballene gets into hydrotalcite layers, d
003Interlamellar spacing further is increased to 2.04nm.In addition, the hydrotalcite ultraviolet-visible spectrogram behind contrast soccerballene and the load soccerballene is found load C
60After hydrotalcite the charateristic avsorption band of soccerballene has also appearred near 239nm, 316nm place, this also shows soccerballene load success.
Embodiment 2
Steps A: take by weighing 15.4g Mg (NO
3)
26H
2O and 11.3g Al (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Water preparation mixing salt solution, other gets 2.0g NaOH and is dissolved in 50ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2The two methods of dripping of protection employing add salts solution and alkaline solution in the four-hole bottle, and dripping off back use 5mol/LNaOH solution adjust pH is 10, and the following 90 ℃ of crystallization 12h of gained slurries, product put into whizzer centrifugal 3min under rotating speed 3500 commentaries on classics/min, spend CO again
2Water washing is to neutral; Take out small amount of sample and characterize behind the dry 20h down for 90 ℃, obtain MgAl-NO
3-LDHs, its Mg
2+/ Al
3+=2.
Step B: with the sodium salt [C of 10.9g naphthylacetic acid
12H
9O
2Na] solid is dissolved in 100mL and removes CO
2Deionized water after change in the four-hole bottle, add again and fill 20g hydrotalcite precursor MgAl-NO
3-LDHs, N
2Protection is heated to 70 ℃, stirs reaction 12h down.Product is put into whizzer centrifugal 3min under rotating speed 3500 commentaries on classics/min, spends CO again
2Water washing is to neutral, and 90 ℃ of following dry 20h can obtain naphthylacetic acid intercalated houghite MgAl-NAA-LDHs.
Step C: with 0.2gC
60Be dissolved in the 100mL YLENE, join again in the four-hole bottle, add naphthylacetic acid intercalated houghite 10g described in the step B, at N
2Protect and also stir down, 70 ℃ are total to hot 48h down, and product is used the YLENE thorough washing, puts into whizzer centrifugal 3min under rotating speed 3500 commentaries on classics/min, behind dry 20h under 90 ℃, can obtain the hydrotalcite MgAl-C of soccerballene and naphthylacetic acid intercalation
60/ NNA-LDHs.
In the present embodiment, the product chemical formula is: [(Mg
2+)
0.67(Al
3+)
0.33(OH)
2]
0.33+(NAA
-)
0.33(C
60)
0.106H
2O.Can be known that by X-ray diffractogram hydrotalcite has comparatively ideal six side's laminate structures, crystalline phase is single, and percent crystallinity is better.The d of naphthylacetic acid intercalated houghite
003Interlamellar spacing is 1.93nm, than intercalation precursor NO
3The interlamellar spacing of-LDH increases 1.04nm.This laminate expansion phenomenon shows that naphthylacetic acid successfully inserts the LDH interlayer.After soccerballene gets into hydrotalcite layers, d
003Interlamellar spacing further is increased to 2.05nm.In addition, the hydrotalcite ultraviolet-visible spectrogram behind contrast soccerballene and the load soccerballene, the charateristic avsorption band of soccerballene has also appearred in the hydrotalcite after the discovery load near 239nm, 316nm, and this also shows soccerballene load success.
Embodiment 3
Steps A: take by weighing 17.5g Co (NO
3)
26H
2O, 11.3g Al (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Water preparation mixing salt solution, other gets 8.0g NaOH and is dissolved in 50ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2Protection adopts two methods of dripping that salts solution and alkaline solution are added in the four-hole bottle violent stirring.Using 2.0mol/LNaOH solution to regulate the pH value is 7.The gained slurries are in 70 ℃ of crystallization 36h, and product is put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spends CO again
2Water washing is to neutral; Take out sample and characterize behind the dry 36h down for 60 ℃, obtain CoAl-NO
3-LDHs, its Co
2+/ Al
3+=2.
Step B: with the sodium salt [C of 10.9g naphthylacetic acid
12H
9O
2Na] solid is dissolved in 100mL and removes CO
2Deionized water after change in the four-hole bottle, add again and fill 20g hydrotalcite precursor ZnAl-NO
3-LDHs, N
2Protection is heated to 60 ℃, stirs reaction 36h down.Product is put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spends CO again
2Water washing is to neutral, and 80 ℃ of following dry 24h can obtain naphthylacetic acid intercalated houghite CoAl-NAA-LDHs.
Step C: with 0.16gC
60Be dissolved in the 100mL YLENE, join in the four-hole bottle, add the 10g of naphthylacetic acid intercalated houghite described in the step B again, at N
2Protect and also stir down, 60 ℃ are total to hot 36h down, and product is used the YLENE thorough washing, puts into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, behind dry 36h under 60 ℃, can obtain the hydrotalcite CoAl-C of soccerballene and naphthylacetic acid intercalation
60/ NNA-LDHs.
In the present embodiment, the product chemical formula is: [(Co
2+)
0.67(Al
3+)
0.33(OH)
2]
0.33+(NAA
-)
0.33(C
60)
0.086H
2O.Can be known that by X-ray diffractogram hydrotalcite has comparatively ideal six side's laminate structures, crystalline phase is single, and percent crystallinity is better.The d of naphthylacetic acid intercalated houghite (CoAl-NAA-LDHs)
003Interlamellar spacing is 1.94nm, than intercalation precursor CoAl-NO
3The interlamellar spacing of-LDHs increases 1.05nm.This laminate expansion phenomenon shows that naphthylacetic acid successfully inserts the LDH interlayer.After soccerballene gets into hydrotalcite layers, d
003Interlamellar spacing further is increased to 2.04nm.In addition, the hydrotalcite ultraviolet-visible spectrogram behind contrast soccerballene and the load soccerballene is found load C
60After hydrotalcite the charateristic avsorption band of soccerballene has also appearred near 239nm, 316nm place, this also shows soccerballene load success.
Embodiment 4
Steps A: take by weighing 17.4g Ni (NO
3)
26H
2O, 11.3g Al (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Water preparation mixing salt solution, other gets 5.6g NaOH and is dissolved in 50ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2Protection adopts two methods of dripping that salts solution and alkaline solution are added in the four-hole bottle violent stirring.Using 3.0mol/LNaOH solution to regulate the pH value is 7.The gained slurries are in 80 ℃ of crystallization 30h, and product is put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spends CO again
2Water washing is to neutral; Take out sample and characterize behind the dry 48h down for 50 ℃, obtain NiAl-NO
3-LDHs, its Ni
2+/ Al
3+=2.
Step B: with the sodium salt [C of 10.9g naphthylacetic acid
12H
9O
2Na] solid is dissolved in 100mL and removes CO
2Deionized water after change in the four-hole bottle, add again and fill 20g hydrotalcite precursor NiAl-NO
3-LDHs, N
2Protection is heated to 60 ℃, stirs reaction 36h down.Product is put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spends CO again
2Water washing is to neutral, and 80 ℃ of following dry 24h can obtain naphthylacetic acid intercalated houghite NiAl-NAA-LDHs.
Step C: with 0.1gC
60Be dissolved in the 100mL YLENE, add in the four-hole bottle, add the 10g of naphthylacetic acid intercalated houghite described in the step B again, at N
2Protect and also stir down, 70 ℃ are total to hot 24h down, and product is used the YLENE thorough washing, puts into whizzer centrifugal 3min under rotating speed 3500 commentaries on classics/min, behind dry 36h under 60 ℃, can obtain the hydrotalcite NiAl-C of soccerballene and naphthylacetic acid intercalation
60/ NNA-LDHs.
In the present embodiment, the product chemical formula is: [(Ni
2+)
0.67(Al
3+)
0.33(OH)
2]
0.33+(NAA
-)
0.33(C
60)
0.056H
2O.Can be known that by X-ray diffractogram hydrotalcite has comparatively ideal six side's laminate structures, crystalline phase is single, and percent crystallinity is better.The d of naphthylacetic acid intercalated houghite (NiAl-NAA-LDHs)
003Interlamellar spacing is 1.94nm, than intercalation precursor NiAl-NO
3The interlamellar spacing of-LDHs increases 1.05nm.This laminate expansion phenomenon shows that naphthylacetic acid successfully inserts the LDH interlayer.After soccerballene gets into hydrotalcite layers, d
003Interlamellar spacing further is increased to 2.04nm.In addition, the hydrotalcite ultraviolet-visible spectrogram behind contrast soccerballene and the load soccerballene is found load C
60After hydrotalcite the charateristic avsorption band of soccerballene has also appearred near 239nm, 316nm place, this also shows soccerballene load success.
Embodiment 5
Steps A: take by weighing 16.4g ZnCl
2With 14.5g AlCl
36H
2O is dissolved in 200ml and removes CO
2Water preparation mixing salt solution, other gets 4.0g NaOH and is dissolved in 100ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2The two methods of dripping of protection employing add salts solution and alkaline solution in the four-hole bottle, and dripping off back use 0.5mol/LNaOH solution adjust pH is 6, and the following 70 ℃ of crystallization 24h of gained slurries, product put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spend CO again
2Water washing is to neutral; Take out small amount of sample and characterize behind the dry 24h down for 70 ℃, obtain ZnAl-Cl-LDHs, its Zn
2+/ Al
3+=2.
Step B: with the sodium salt [C of 10.9g naphthylacetic acid
12H
9O
2Na] solid is dissolved in 100mL and removes CO
2Deionized water after change in the four-hole bottle, add again and fill 20g hydrotalcite precursor ZnAl-Cl-LDHs, N
2Protection is heated to 70 ℃, stirs reaction 36h down.Product is put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spends CO again
2Water washing is to neutral, and 70 ℃ of following dry 20h can obtain naphthylacetic acid intercalated houghite ZnAl-NAA-LDHs.
Step C: 0.1gC60 is dissolved in the 100mL YLENE, adds again in the four-hole bottle, add naphthylacetic acid intercalated houghite 10g described in the step B, at N
2Protect and also stir down, 70 ℃ are total to hot 36h down, and product is used the YLENE thorough washing, puts into whizzer centrifugal 3min under rotating speed 3500 commentaries on classics/min, behind dry 20h under 70 ℃, can obtain the hydrotalcite ZnAl-C of soccerballene and naphthylacetic acid intercalation
60/ NNA-LDHs.
In the present embodiment, the product chemical formula is: [(Zn
2+)
0.67(Al
3+)
0.33(OH)
2]
0.33+(NAA
-)
0.33(C
60)
0.054H
2O.Can be known that by X-ray diffractogram hydrotalcite has comparatively ideal six side's laminate structures, crystalline phase is single, and percent crystallinity is better.The d of naphthylacetic acid intercalated houghite
003Interlamellar spacing is 1.94nm, than intercalation precursor NO
3The interlamellar spacing of-LDH increases 1.05nm.This laminate expansion phenomenon shows that naphthylacetic acid successfully inserts the LDH interlayer.After soccerballene gets into hydrotalcite layers, d
003Interlamellar spacing further is increased to 2.04nm.In addition, the hydrotalcite ultraviolet-visible spectrogram behind contrast soccerballene and the load soccerballene, the charateristic avsorption band of soccerballene has also appearred in the hydrotalcite after the discovery load at 239nm, 316nm place, and this also shows soccerballene load success.
Embodiment 6
Steps A: take by weighing 26.4g Zn (NO
3)
26H
2O, 11.3g Al (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Water preparation mixing salt solution, other gets 10.0g NaOH and is dissolved in 50ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2Protection adopts two methods of dripping that salts solution and alkaline solution are added in the four-hole bottle violent stirring.Using 1.0mol/LNaOH solution to regulate the pH value is 7.The gained slurries are in 60 ℃ of crystallization 48h, and product is put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spends CO again
2Water washing is to neutral; Take out sample and characterize behind the dry 24h down for 70 ℃, obtain ZnAl-NO
3-LDHs, its Zn
2+/ Al
3+=3.
Step B: with the sodium salt [C of 10.9g naphthylacetic acid
12H
9O
2Na] solid is dissolved in 100mL and removes CO
2Deionized water after change in the four-hole bottle, add again and fill 20g hydrotalcite precursor ZnAl-NO
3-LDHs, N
2Protection is heated to 60 ℃, stirs reaction 36h down.Product is put into whizzer centrifugal 4min under rotating speed 3000 commentaries on classics/min, spends CO again
2Water washing is to neutral, and 80 ℃ of following dry 24h can obtain naphthylacetic acid intercalated houghite ZnAl-NAA-LDHs.
Step C: with 0.1gC
60Be dissolved in the 100mL YLENE, add in the four-hole bottle, add the 10g of naphthylacetic acid intercalated houghite described in the step B again, at N
2Protect and also stir down, 55 ℃ are total to hot 48h down, and product is used the YLENE thorough washing, puts into whizzer centrifugal 3min under rotating speed 3500 commentaries on classics/min, behind dry 20h under 70 ℃, can obtain the hydrotalcite ZnAl-C of soccerballene and naphthylacetic acid intercalation
60/ NNA-LDHs.
In the present embodiment, the product chemical formula is: [(Zn
2+)
0.75(Al
3+)
0.25(OH)
2]
0.25+(NAA
-)
0.25(C
60)
0.055H
2O.Can be known that by X-ray diffractogram hydrotalcite has comparatively ideal six side's laminate structures, crystalline phase is single, and percent crystallinity is better.The d of naphthylacetic acid intercalated houghite (ZnAl-NAA-LDHs)
003Interlamellar spacing is 1.94nm, than intercalation precursor ZnAl-NO
3The interlamellar spacing of-LDHs increases 1.05nm.This laminate expansion phenomenon shows that naphthylacetic acid successfully inserts the LDH interlayer.After soccerballene gets into hydrotalcite layers, d
003Interlamellar spacing further is increased to 2.04nm.In addition, the hydrotalcite ultraviolet-visible spectrogram behind contrast soccerballene and the load soccerballene is found load C
60After hydrotalcite the charateristic avsorption band of soccerballene has also appearred near 239nm, 316nm place, this also shows soccerballene load success.
Claims (4)
1. the hydrotalcite material of a load high dispersion fullerene; It is characterized in that: prepare the hydrotalcite precursor earlier,, form the hydrophobic environment that contains a large amount of naphthylene groups at interlayer again with naphthylacetic acid root intercalated houghite; Then soccerballene is fixed in hydrotalcite layers, the chemical formula of hydrotalcite material is:
[(M
2+)
1-x(M
3+)
x(OH)
2]
x+(NAA
-)
x(C
60)
y·mH
2O
X=0.25～0.33 wherein, y=0.05～0.1, m=3～6, m is the quantity of interlayer crystal water molecule, M
2+Be divalent-metal ion, M
3+Be trivalent metal ion Al
3+
2. the hydrotalcite material of load high dispersion fullerene according to claim 1 is characterized in that: said M
2+Be Mg
2+, Ni
2+, Zn
2+Or Co
2+
3. the hydrotalcite material of load high dispersion fullerene according to claim 2 is characterized in that: said M
2+Be Ni
2+Or Zn
2+
4. a method for preparing the hydrotalcite material of the described load high dispersion fullerene of claim 1 is characterized in that comprising the steps:
The preparation of A, hydrotalcite precursor:
With M
2+Soluble salt and Al
3+Soluble salt be mixed with mixing solutions, M wherein
2+/ Al
3+Mol ratio is 2～3, M
2+Volumetric molar concentration be 0.1～1.0M, Al
3+Volumetric molar concentration be 0.05～0.5M; With NaOH is alkaline solution, and wherein the NaOH volumetric molar concentration is 1.0～5.0M, at room temperature N
2Under the protective condition, adopt two methods that salts solution and alkaline solution are added in the four-hole bottle, using 0.1～5.0M NaOH solution adjust pH again after adding is accomplished is 6～10, and with 60～90 ℃ of crystallization 12～72h of gained slurries, product is centrifugal, washing is extremely neutral; Take out 50～90 ℃ of down dry 20～48h of sample, obtain the hydrotalcite precursor;
Described M
2+Soluble salt be hydrochloride or nitrate salt, Al
3+Soluble salt be hydrochloride or nitrate salt, and M
2+Soluble salt and Al
3+The kind of soluble salt identical;
B, naphthylacetic acid root intercalated houghite:
Nafusaku is dissolved in removes CO
2Deionized water in, the hydrotalcite precursor that again steps A is obtained joins in this solution, N
2Protection is heated to 50～70 ℃, reaction 12～48h, and product is centrifugal, washing is extremely neutral, and 50～90 ℃ of down dry 20～48h can obtain the naphthylacetic acid intercalated houghite;
C, soccerballene are fixed in hydrotalcite layers:
The soccerballene crystal is dissolved in the YLENE, adds the naphthylacetic acid intercalated houghite that step B obtains, at N
2Protection is total to heat 12～48h down under 50～70 ℃, product can obtain the hydrotalcite of soccerballene and naphthylacetic acid intercalation with YLENE thorough washing, centrifugal behind 50～90 ℃ of down dry 20～48h.
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