CN108873557A - A kind of optical material and preparation method thereof - Google Patents
A kind of optical material and preparation method thereof Download PDFInfo
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- CN108873557A CN108873557A CN201810809188.2A CN201810809188A CN108873557A CN 108873557 A CN108873557 A CN 108873557A CN 201810809188 A CN201810809188 A CN 201810809188A CN 108873557 A CN108873557 A CN 108873557A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3619—Organometallic compounds
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Abstract
The present invention proposes a kind of optical material, for by TCPP and Preyssler type polyoxometallate P5W30Intercalation enters Mg altogether2Al‑NO3Product (P obtained in hydrotalcite5W30)x‑(TCPP)y/Mg2Al is total to intercalated compound, wherein x/y represents P in product5W30With the mass ratio of the material of TCPP；x/y=0~30/35.Preferably, x/y=25.34/35.The present invention also proposes the preparation method of the optical material.The present invention passes through TCPP and P5W30Intercalation enters Mg altogether2Al‑NO3In hydrotalcite, there is the two can in carrier jointly and forms the third-order nonlinear optical response that improve material to acceptor systems, optical effect is good.
Description
Technical field
The invention belongs to nonlinear optical material field more particularly to a kind of optical material (P5W30)x-(TCPP)y/Mg2Al
Intercalated compound and preparation method thereof altogether.
Background technique
Material with nonlinear optical property and fast response time under lasing condition has gradually obtained the wide of people
General concern, nonlinear material all have important in various fields such as optical communication, lasing safety, optical information processing, optical medicals
Using.Nonlinear optical material will not only have stronger nonlinear response and shorter response time in practical applications, also
Have many advantages, such as that optical loss is small, stability is high, at low cost easily prepared.
Organic non linear optical material it is non-linear strong, the response time is short, and damage threshold is larger, and organic material can be with
It is designed and modifies in molecular level, therefore organic non linear optical material is answered in terms of non-linear field there is huge
Use potentiality.Wherein, porphyrin is formed by four pyrrole units by methine bridging, and porphyrin itself includes big pi-conjugated system, in ring
There are 18 conjugated electrons, there is height conjugacy, and be easy to be modified on the ring of porphyrin, Porphyrin Molecule is a kind of good electricity
Sub- donor, thus porphyrin shows excellent non-linear optical property and fast response speed.In addition to this, good chemistry
Stability and thermal stability, be easy to the advantages that forming a film also and make its non-linear optical field have it is huge can tap value.
So far, people improve the third-order non-linear response of porphyrins in several ways, such as to porphyrin
The modification of ring regulates and controls its third-order non-linear by introducing other groups, when result of study shows that substituent group is electron-withdrawing group
The non-linear susceptibility of porphyrin can be reduced, electron donating group substituent group can then improve the non-linear susceptibility of porphyrin, and substituent group
Easier electron is bigger to the amplification of porphyrin third-order nonlinear susceptibility.And different the position of substitution pair is thirdly rank is non-thread
Property polarizability χ can equally have an impact, and be to the affecting laws of χ when substituent group is electron donating group:Ortho position>Contraposition>Meta position.But
It is that the research and development to this kind of materials are still not up to practical application level so far, that is, is greater than 10-8esu.In addition to this, porphyrin is formed
Polymer is also the important means for improving the response of porphyrin material third-order non-linear, and porphyrin polymer is compared to porphyrin and its derivative
Conjugacy is stronger for object, therefore also stronger compared to the transfer ability of the energy of monomer and electronics, the electronics of porphyrin polymer
Delocalization is clearly more powerful, this makes electronics transfer between monomer and interaction more obvious, and HOMO-LUMO can be effectively reduced
Energy gap.However, porphyrin polymer synthesis condition is harsh, it is difficult to isolate and purify, yield is lower, and Characterization of The Products is difficult, dissolubility and
The disadvantages of machinability is poor limits the practical application of porphyrin polymer.
In addition, porphyrin, as a kind of organic material, the defects such as dissolubility is poor, material transmissivity is low limit it and answer
With, and limited by organic matter self character, the raising of the nonlinear response of simple porphyrin material has reached bottleneck, i.e.,
Make to be formed porphyrin polymer its non-linear nature to be also difficult to be greatly improved, therefore in order to further enhance three ranks of material
Nonlinear response needs to introduce inorganic component formation hybrid system in porphyrin system, to make up porphyrin conduct
Defect existing for organic non linear optical material improves its nonlinear response.
Polyoxometallate (Polyoxometalates, POMs), which refers to, to be combined transiting state metal ion by oxygen to be formed
Multi-metal oxygen cluster compound.Polyacid favorable solubility and is soluble in polar organic solvent in water；Carry electron amount, substance
Configuration is larger with difference in size, can carry out the regulation of small particle level；It is easy to receive electronics, can be combined with organic electronic donor
It is formed to acceptor systems.Therefore polyacid and porphyrin are formed to that can promote electronics transfer after acceptor systems under lasing condition, are increased
Strong electron mobility, and then improve the Nonlinear Third-Order Optical Properties of material.However, anionic porphyrin and polyoxoanion because
Like charges are carried so that will receive the influence of charge repulsion each other in solution, therefore can not be formed to acceptor systems, resistance
Charge between the two and energy transfer are hindered.Therefore the ion-exchangeable carrier of one kind can be found to load anionic porphin
Quinoline and polyoxoanion make the two that can there is jointly formation to acceptor systems in carrier, and then three ranks for improving material are non-thread
Property optic response.
Summary of the invention
To solve the deficiencies in the prior art, the present invention proposes a kind of optical material, passes through TCPP and P5W30Intercalation enters altogether
Mg2Al-NO3In hydrotalcite, there is the two can in carrier jointly and is formed to acceptor systems, three ranks for improving material are non-thread
Property optic response, optical effect are good.The present invention also proposes the preparation method of the optical material.Concrete scheme of the invention is as follows：
The present invention proposes a kind of optical material, for by TCPP and Preyssler type polyoxometallate P5W30Intercalation enters altogether
Mg2Al-NO3Product (P obtained in hydrotalcite5W30)x-(TCPP)y/Mg2Al is total to intercalated compound, and the TCPP is four (right
Carboxyl phenyl) porphyrin, the P5W30For K12.5Na1.5[NaP5W30O110]·15H2O, the Mg2Al-NO3For nitrate anion magnesium
Aluminum hydrotalcite；Wherein, x represents P in product5W30Substance amount, y represents the amount of the substance of TCPP in product, and x/y represents product
Middle P5W30With the mass ratio of the material of TCPP；X/y=0~30/35.
Preferably, the x/y=25.34/35.
The present invention also proposes a kind of preparation method of above-mentioned optical material, includes the following steps：
The preparation of S1.TCPP
P formylbenzoic acid 16g is dissolved in 500ml propionic acid, heating reaches reflux, and 7.40mL pyrroles is added dropwise, and protects
Hold reflux 1h；After the reaction was completed, it filters while hot, obtained solid first uses 160mLCH2Cl2Rinse, again with 40mL tetrahydrofuran flushing,
Dry gained precipitating, is recrystallized, product is purple powder in the mixed liquor of methanol and methylene chloride.
S2.P5W30Preparation
In 30mLH2The Disodium tungstate (Na2WO4) dihydrate of 33g is dissolved in O, and the phosphoric acid of 26.5ml is added thereto and is stirred evenly, it will
Acquired solution moves into 100ml reaction kettle, reacts for 24 hours at 120 DEG C, reaction kettle is down to room temperature after the completion, by gained mixture
It moves in beaker, adds 15mL deionized water and 10g potassium chloride thereto, be filtered under diminished pressure, obtained solid 30mL 2M potassium acetate
Solution rinses, then with 30mL CH3OH is rinsed, and obtains crude product, is recrystallized after crude product is dried with 200ml hot water,
Obtain clean product.
S3.Mg2Al-NO3The preparation and removing of hydrotalcite
Select constant pH coprecipitation Mg2Al-NO3Hydrotalcite：5.1g six is added into 30mL deionized water and is hydrated nitre
Sour magnesium and 3.7g ANN aluminium nitrate nonahydrate；4g NaOH is dissolved in 50mL deionized water, precipitating reagent is made；Under nitrogen protection, to
25mL is pre-adjusted in the deionized water of pH to 9.5 and is slowly added in the mixed solution of magnesium nitrate and aluminum nitrate, is being vigorously stirred
In the case where so that pH is maintained at 9.5, after dripping off, be warming up to 70 DEG C and continue stir 60min, heat preservation for 24 hours, mixture is centrifuged,
Supernatant liquid is removed, then obtained solid is dried in vacuo for 24 hours with a small amount of hot water injection；By gained 2.0g Mg2Al-NO3Hydrotalcite
It grinds.
Remove Mg2Al-NO3When hydrotalcite, the above-mentioned hydrotalcite of 0.4g is added simultaneously into 400ml formamide under nitrogen protection
It persistently stirs two days, Mg is prepared2Al-NO3Hydrotalcite colloid.
S4. the preparation of intercalated compound powder and mixed solution
It is put into TCPP into 50ml water, the sodium hydroxide solution of 1M is added until TCPP is completely dissolved, pH=7.8-8.2,
Add P5W30, then under nitrogen protection, it is slowly added to the Mg that 20mL has been removed thereto2Al-NO3Colloid stirs 20min
After be centrifuged, after centrifugation solid with hot water wash three times, in 80 DEG C of dry 48h, P5W30The mass ratio of the material with TCPP is x/y=
0~30/35, by adjusting different the mass ratio of the materiaies, obtain different P5W30(the P of/TCPP ratio5W30)x-(TCPP)y/Mg2Al
Intercalated compound powder altogether.
By the different P5W30(the P of/TCPP ratio5W30)x-(TCPP)y/Mg2Al be total to intercalated compound powder spend from
Sub- water dissolution, obtains corresponding P5W30The intercalated compound mixed solution of/TCPP the mass ratio of the material, the i.e. optical material.
The principle of the present invention and beneficial effect：
P of the invention5W30Polyacid favorable solubility and is soluble in polar organic solvent in water；Carry electron amount, object
Texture type and difference in size are larger, can carry out the regulation of small particle level；It is easy to receive electronics, can be mutually tied with organic electronic donor
It closes and is formed to acceptor systems.Therefore P5W30It is formed with TCPP to electronics transfer can be promoted after acceptor systems under lasing condition,
Enhance electron mobility, and then improves the Nonlinear Third-Order Optical Properties of material.The interlayer of hydrotalcite stratified material has ion
Exchange interaction can coexist in same interlayer there are many different anions, therefore can be total to intercalation to the interlayer of hydrotalcite material
Porphyrin anion and polyoxoanion, not only can solve anion not of the same race in the solution can not be into due to charge repulsion
Electronics can also occur between the different anions of same layer and energy transmission acts on the problem of row interaction, and in different layer
Anion equally can be to impacting one another, to further enhance the third-order nonlinear optical response of compound.Two kinds of yin
Ion can pass through the ratio both in the polyoxoanion and porphyrin anion layer of adjusting addition when hydrotalcite layers are total to intercalation
Example, to adjust the third-order non-linear response of material, so as to meet the different demands to material.
Detailed description of the invention
Fig. 1 is the intercalated compound and Mg of the intercalated compound of embodiment 1, embodiment 172Al-NO3The X-ray of hydrotalcite
Diffraction pattern.
Fig. 2 is arrangement mode schematic diagram of the TCPP between intercalation.
Fig. 3 is P5W30Arrangement mode schematic diagram between intercalation.
Fig. 4 is the X-ray diffractogram of 1-17 intercalated compound powder of embodiment.
Fig. 5 is TCPP and P in intercalated compound5W30Arrangement mode schematic diagram.
Fig. 6 is the mono- intercalated compound of TCPP, TCPP and Mg of embodiment 12Al-NO3The infrared spectroscopy of hydrotalcite.
Fig. 7 is the P of embodiment 175W30、P5W30Single intercalated compound and Mg2Al-NO3The infrared spectroscopy of hydrotalcite.
Fig. 8 be embodiment 1-17 on P5W30- TCPP is total to the infrared spectrum of intercalated compound.
Fig. 9 is the P of embodiment 1-165W30The aperture of the Z- scanning curve of/TCPP mixed solution under 532nm laser is bent
Line.
Figure 10 is the P of embodiment 1-165W30The closed pore of the Z- scanning curve of/TCPP mixed solution under 532nm laser is bent
Line.
Figure 11 is the P of embodiment 175W30The aperture of Z- scanning curve of single intercalated compound suspension under 532nm laser
Curve.
Figure 12 is the P of embodiment 175W30The closed pore of Z- scanning curve of single intercalated compound suspension under 532nm laser
Curve.
Figure 13 is the aperture curve of Z- scanning curve of the solvent ethylene glycol under 532nm laser.
Figure 14 is the closed pore curve of Z- scanning curve of the solvent ethylene glycol under 532nm laser.
Figure 15 is the P of embodiment 1-175W30The uv atlas of intercalated compound suspension sample is total to TCPP.
Figure 16 is that the aperture of Z- scanning curve of the suspension of the intercalated compound of embodiment 1-16 under 532nm laser is bent
Line.
Figure 17 is that the closed pore of Z- scanning curve of the suspension of the intercalated compound of embodiment 1-16 under 532nm laser is bent
Line.
Figure 18 is the relative size of the third-order nonlinear optical parameter of the suspension of the intercalated compound of embodiment 1-16.
Specific embodiment
As follows in conjunction with attached drawing, application scheme is further described：
A kind of optical material, for by TCPP and Preyssler type polyoxometallate P5W30Intercalation enters Mg altogether2Al-NO3Water
Product (P obtained in talcum5W30)x-(TCPP)y/Mg2Al is total to intercalated compound, and the TCPP is four (to carboxyl phenyl) porphins
Quinoline, the P5W30For
K12.5Na1.5[NaP5W30O110]·15H2O, the Mg2Al-NO3For nitrate anion magnalium hydrotalcite；Wherein, x generation
P in table product5W30Substance amount, y represents the amount of the substance of TCPP in product, and x/y represents P in product5W30With the object of TCPP
The amount ratio of matter；X/y=0~30/35.
A kind of preparation method of above-mentioned optical material, includes the following steps：
The preparation of S1.TCPP
P formylbenzoic acid 16g is dissolved in 500ml propionic acid, heating reaches reflux, and 7.40mL pyrroles is added dropwise, and protects
Hold reflux 1h；After the reaction was completed, it filters while hot, obtained solid first uses 160mLCH2Cl2Rinse, again with 40mL tetrahydrofuran flushing,
Dry gained precipitating, is recrystallized in the mixed liquor of methanol and methylene chloride, and product is purple powder, and 4.4g is made and produces
Object, yield 25%.Infrared spectroscopy/cm-1:3429 (ν COOH stretching vibrations)；3317,1699 (s C=O stretching vibrations)；
1602-1400 (stretching vibration of s phenyl ring skeleton)；1276-1173 (ν C-O stretching vibration)；1016 (the flexible vibrations of m porphyrin ring skeleton
It is dynamic).Nucleus magnetic hydrogen spectrum (DMSO):8.2[8H,Ar(CH.N.CH)]；8.14(8H,βH)；-2.2(2H,-NH).
S2.P5W30Preparation
In 30mLH2The Disodium tungstate (Na2WO4) dihydrate of 33g is dissolved in O, and the phosphoric acid of 26.5ml is added thereto and is stirred evenly, it will
Acquired solution moves into 100ml reaction kettle, reacts for 24 hours at 120 DEG C, reaction kettle is down to room temperature after the completion, by gained mixture
It moves in beaker, adds 15mL deionized water and 10g potassium chloride thereto, be filtered under diminished pressure, obtained solid 30mL 2M potassium acetate
Solution rinses, then with 30mL CH3OH is rinsed, and obtains crude product, is recrystallized after crude product is dried with 200ml hot water,
Obtain clean product 6.0g.Infrared spectroscopy/cm-1:1167cm-1,1081cm-1, 1020cm-1(P-O stretching vibration)；938cm-1(W
=O stretching vibration)；913cm-1, 789cm-1(W–O–W)。
S3.Mg2Al-NO3The preparation and removing of hydrotalcite
Select constant pH coprecipitation Mg2Al-NO3Hydrotalcite：5.1g six is added into 30mL deionized water and is hydrated nitre
Sour magnesium and 3.7g ANN aluminium nitrate nonahydrate；4g NaOH is dissolved in 50mL deionized water, precipitating reagent is made；Under nitrogen protection, to
25mL is pre-adjusted in the deionized water of pH to 9.5 and is slowly added in the mixed solution of magnesium nitrate and aluminum nitrate, is being vigorously stirred
In the case where so that pH is maintained at 9.5, after dripping off, be warming up to 70 DEG C and continue stir 60min, heat preservation for 24 hours, mixture is centrifuged,
Supernatant liquid is removed, then obtained solid is dried in vacuo for 24 hours with a small amount of hot water injection；By gained 2.0g Mg2Al-NO3Hydrotalcite
It grinds.
Remove Mg2Al-NO3When hydrotalcite, the above-mentioned hydrotalcite of 0.4g is added simultaneously into 400ml formamide under nitrogen protection
It persistently stirs two days, Mg is prepared2Al-NO3Hydrotalcite colloid.
S4. the preparation of intercalated compound powder and mixed solution
It is put into TCPP into 50ml water, the sodium hydroxide solution of 1M is added until TCPP is completely dissolved, pH=7.8-8.2,
Add P5W30, then under nitrogen protection, it is slowly added to the Mg that 20mL has been removed thereto2Al-NO3Colloid stirs 20min
After be centrifuged, after centrifugation solid with hot water wash three times, in 80 DEG C of dry 48h, P5W30The mass ratio of the material with TCPP is x/y=
0~30/35, by adjusting different the mass ratio of the materiaies, obtain different P5W30(the P of/TCPP ratio5W30)x-(TCPP)y/Mg2Al
Intercalated compound powder altogether, such as the following table 1 embodiment 1-17.
By the different P5W30(the P of/TCPP ratio5W30)x-(TCPP)y/Mg2Al be total to intercalated compound powder spend from
Sub- water dissolution, obtains corresponding P5W30The intercalated compound mixed solution of/TCPP the mass ratio of the material, as shown in table 1 below.
1. difference P of table5W30The intercalated compound preparation parameter and composition of/TCPP the mass ratio of the material
The associated products of above-mentioned preparation are detected, it is as a result as follows：
1, the composition measuring (XRD spectra) of intercalated compound
In order to calculate different charge ratios compound molecular formula, the present invention carried out ICP- to synthesized compound
AES elemental analysis and the analysis test of hydrocarbon nitrogen, the composition of total intercalated compound have been calculated according to acquired results, specific number
According to being shown in Table in 1.From data in table 1 it is found that Mg/Al ratio is approximately equal to the Mg/Al ratio in raw material hydrotalcite in compound
(ICP result Mg/Al=2.05), further demonstrates that hydrotalcite still keeps original structure.The ratio of W/P in compound 6 or so,
With P5W30In W/P ratio it is close, show P5W30Anion still keeps original structure in the composite.Due to adding when synthesising complex
The P entered5W30It is different from the ratio of TCPP, therefore P in products therefrom5W30It is also different from the ratio of TCPP, with P5W30Dosage
Increase, the P in compound5W30Content also gradually increases, and the content of the TCPP in compound is then accordingly reduced.It is actually inserted into
Mg2The P of Al hydrotalcite layers5W30The mass ratio of the material of/TCPP is greater than addition value, this may be due to P5W30The exchange of anion
Ability is significantly stronger than TCPP, and reason is mainly P5W30The charge number of carrying is much higher than TCPP.
As shown in Figure 1, (a) is TCPP in embodiment 1 in Mg2The powder X-ray RD spectrogram of single intercalated compound in Al, (c)
For the XRD spectra of Mg2Al-NO3 hydrotalcite.It can be seen that there is (003) of single magnalium hydrotalcite in 2 θ=3.7 ° positions
Diffraction maximum, illustrate product be it is single-phase, can calculate interlamellar spacing by Bragg equation 2dsin θ=λ isBy thicknessKnow that layer inner height is after deduction In zinc-aluminum hydrotalcite when intercalation TCPP, when hydrotalcite layers distance isWhen TCPP arranged in such a way that double layer planarization porphin ring is parallel to laminate, so herein TCPP should be equally with double
The mode that planarizing layers, that is, pyrrole ring is parallel to laminate arranges, as shown in Figure 2.
As shown in Figure 1, (b) being P in embodiment 175W30The powder X-ray RD spectrogram of single intercalated compound is shown in 2 θ=6.1 °
(003) diffraction maximum of single magnalium hydrotalcite out, illustrate product be it is single-phase, by calculate known to interfloor distance be about
Left and right, and P5W30Polyanionic is in C5Length in axis direction is aboutIt can be inferred that its arrangement mode in layer is C5
Axis is perpendicular to neatly stone veneer, as shown in Figure 3.Therefore, P5W30Polyanionic is in Mg2Ten divider of arrangement in Al neatly stone veneer
Then.And former Mg is not observed in figure2NO in Al hydrotalcite3 -The characteristic diffraction peak of anion illustrates the side by remove-accumulating again
Nitrate anion and carbonate in the intercalated compound of method preparation are gone out by complete exchange.
It is illustrated in figure 4 the XRD diagram of 1-17 intercalated compound powder of embodiment, with P in compound5W30Polyanionic
The increase of content and the reduction of TCPP content, the diffraction maximum of compound are gradually changed into from the characteristic diffraction peak based on TCPP
P5W30Characteristic diffraction peak based on polyanionic.All compounds show single (003) diffraction maximum, illustrate that product is
It is single-phase, adequately prove that two kinds of anion coexist in identical layer.With P5W30Polyanionic is in Mg2In Al neatly stone veneer layer
Content slowly increase, interlamellar spacing, which slowly decreases up to, to be reachedLeft and right, at this moment TCPP is i.e. double from double layer planarization in interlayer
The arrangement mode that layer porphin ring is parallel to laminate becomes single layer planarization arrangement mode, as shown in Figure 5.(110) Mg at2Al water
Talcum diffraction maximum gradually weakens until disappearing, this may be since the content of polyacid gradually increases, so that interlayer is in acyclic acidic
Border, to reduce the crystallinity of material.
2, infrared spectrum measurement
Fig. 6 is the mono- intercalated compound of TCPP, TCPP and Mg of embodiment 12Al-NO3The infrared spectroscopy of hydrotalcite.It can in figure
To find out, the mono- intercalated compound 1 of TCPP has the key band of TCPP, Mg occurs in the position 446cm-12The O- of Al hydrotalcite
The appearance of the vibrational band of M-O, this feature bands of a spectrum shows Mg2Al hydrotalcite main structure keeps complete.1542cm-1 and
The vibrational band of 1390cm-1 shows that deprotonation has occurred in the part carboxyl on TCPP, these band positions relative to
Minute movement has occurred in TCPP, this is because there is interactions between the two.
Fig. 7 is the P of embodiment 175W30、P5W30Single intercalated compound and Mg2Al-NO3The infrared spectroscopy of hydrotalcite,
1167cm-1,1081cm-1, 1020cm-1For the vibrational band of the P-O key of polyacid, 938cm-1For the stretching band of W=O,
913cm-1And 789cm-1For the vibrational band of W-O-W key, show P5W30The structure of polyacid is not destroyed, and is deposited between laminate
It is influencing each other.
Fig. 8 be embodiment 1-17 on P5W30- TCPP is total to the infrared spectrum of intercalated compound, from Fig. 8 it can be found that
446cm-1The Mg of position2The vibrational band of the O-M-O of Al hydrotalcite, 1542cm-1And 1390cm-1TCPP carboxyl vibrational band,
In 1167cm-1,1081cm-1, 1020cm-1For the vibrational band of the P-O key of polyacid, 938cm-1For the stretching band of W=O,
913cm-1And 789cm-1Vibrational band for W-O-W key is able to observe that, the P in intercalated compound5W30Content gradually becomes
It is more, P5W30Polyanionic is in 913cm-1And 789cm-1The W-O-W key chattering bands of a spectrum at place, 938cm-1The W=O stretching vibration at place is composed
The key bands such as band gradually increase, and show the P in compound5W30Polyanionic content is more and more, this analysis result
It is consistent with powder X-ray RD result.
3、(P5W30)x-(TCPP)yThe Nonlinear Third-Order Optical Properties of mixed solution
Have studied raw material TCPP and P used in 1-16 of the embodiment of the present invention5W30In aqueous solution with intercalated compound
The Nonlinear Third-Order Optical Properties of the mixed solution of the amount ratio of respective substance, Fig. 9 and 10 are its Z- scanning curve, specifically,
Fig. 9 is P5W30The aperture curve of the Z- scanning curve of/TCPP mixed solution 1-16 at 532nm.Figure 10 is P5W30/ TCPP mixing
The closed pore curve of Z- scanning curve of the solution 1-16 at 532nm.Solid line is fitting data in figure, and imaginary point is experimental data.Table 2
For thirdly rank non-linear optical data.The result shows that with the P being added into solution5W30The increase of amount, solution show non-thread
Property anti-saturated absorption and self-defocusing property, and the third-order non-linear absorption parameter of solution slightly enhances, nonlinear refractive index
It is held essentially constant, which proves that polyoxoanion influences very little to the nonlinear response of porphyrin anion in the solution, main
Want reason may be between two kinds of anion electrostatic repulsion make charge between the two and energy transfer relatively difficult, interact
It is weaker.
The P of table 2, the mass ratio of the material corresponding with serial intercalated compound5W30With the third-order non-linear of TCPP mixed solution
Optical parameter
Note：Solvent is 50ml deionized water, and the sodium hydroxide solution of appropriate 1M is added until TCPP is completely dissolved solution.
4、P5W30The Nonlinear Third-Order Optical Properties of intercalated compound 17 and solvent ethylene glycol
Figure 11-14 is the P of embodiment 175W30Single intercalated compound, that is, P5W30Single intercalated houghite composite sample and solvent
The Z- scanning curve of ethylene glycol.Wherein Figure 11 and 12 is the P of embodiment 175W30The aperture of single intercalated compound suspension and closed pore
Curve, two curve basic horizontals in figure, it was demonstrated that P5W30Single intercalated compound itself has negligible non-linear sound
It answers, further proves P5W30Come with the TCPP third-order non-linear property for being total to intercalated compound multiple in intercalation from TCPP and the two
Close electronics flowing and the energy transfer in object.
It is non-to three rank of intercalated compound to demonstrate solvent ethylene glycol under same experimental conditions using Z- scanning as means again
The influence of linear optics property.As shown in Figs. 13 and 14, under same experiment condition, the Z- scanning curve of ethylene glycol is similarly one
Straight line shows further to prove the third-order nonlinear optical of intercalated compound thirdly rank nonlinear optical response can be ignored
Response comes from TCPP.
The above results show P5W30Third-order nonlinear optical response with solvent ethylene glycol itself can be ignored, and intercalation is multiple
The third-order non-linear property of object is closed from TCPP and TCPP and P5W30Electronics flowing and energy of the two in intercalated compound
Transfer.
5、P5W30)x-(TCPP)yThe Nonlinear Third-Order Optical Properties of/LDH
Figure 15 is the P of embodiment 1-175W30The uv atlas of intercalated compound suspension sample is total to TCPP.It can be seen that
The absorption peak strength of TCPP in the intercalated compound suspension sample of embodiment 1-17 is essentially identical, illustrates TCPP in sample
Concentration is essentially identical, and the uv atlas of intercalated compound suspension is the porphyrin characteristic absorption peak typically replaced without metal, and two
There is high intensity Soret band, μ near 418nm in person2(л)-eg(л*) transition occurs four at 515,550,587 and 643nm
A weak Q band.
The present invention has studied the Nonlinear Third-Order Optical Properties of the intercalated compound suspension of embodiment 1-16, Figure 16 and 17
Aperture and closed pore curve for compound suspension, the third-order nonlinear optical of the suspension of the intercalated compound of embodiment 1-16
Parameter is with addition P5W30It is as shown in figure 18 with the mass ratio of the material change curve of TCPP, (β (esu)/10-6For grid broken line；n2
(esu)/10-10For dot broken line；χ(3)(esu)/10-11For triangle broken line), the Fitting Calculation gained design parameter is shown in Table 3.As a result
Show that intercalated compound and precursor porphyrin TCPP show the property of anti-saturated absorption and self-defocusing.And in compound
P5W30The gradually increasing of amount also results in the nonlinear response of compound and increases, and this is mainly due under laser excitation
P5W30Electronics or energy transmission effect between anion and TCPP anion, and work as P5W30The substance of anion and TCPP anion
Amount than reach x/y=27.5/35 i.e. the intercalated compound of embodiment 13 when, the nonlinear response of material starts to reduce,
Reason may be with Mg2Al hydrotalcite layers P5W30Anion-content gradually increases, and TCPP anion-content gradually decreases, when
Although TCPP anion-content is reduced to a certain amount of P under laser action later5W30Between anion and TCPP anion there are still
Electronics or energy transfer, but since the content of TCPP anion is too small, cause the third-order non-linear of intercalated compound respond by
Gradually reduce.The response of intercalated compound third-order non-linear reaches P when maximum value5W30The amount of the substance of anion and TCPP anion
Than for x/y=25.34/35, that is, intercalated compound 12, this provides foundation for the maximization of material properties and the saving of raw material.
With P5W30Content in the composite gradually increases, and the nonlinear response that intercalated compound is shown first gradually increases
By force, start slowly to reduce again after culminating, prepared TCPP/P before this phenomenon and research5W30/ LDH ultrathin membrane phase
Together, TCPP and P5W30Electron and energy transfer effect can occur under the excitation of laser, so in same layer or different layer or even absorption
In the TCPP and P of neatly stone surface5W30Between all there is electronics and energy transfer phenomenon, reach and increase porphyrin nonlinear response
Purpose.
Table 3, embodiment 1-16 intercalated compound suspension nonlinear parameter
6, conclusion
The intercalated compound (embodiment 1-17) of proportion-controllable is synthesized by removing-restacking method, and to the knot of material
Structure and composition are characterized, and have studied its Nonlinear Third-Order Optical Properties using Z- scan method.According to powder X-ray RD diffraction spectrogram
A layer inner height is calculated, so that it is determined that TCPP is in the mono- intercalated compound of TCPP of embodiment 1 with double layer planarization i.e. pyrrole ring
The mode for being parallel to laminate arranges.And in the P of embodiment 175W30In single intercalated compound, P5W30With C5Axis and laminate Vertical Square
Formula arrangement.The powder X-ray RD diffraction of all compounds all has single (003) diffraction maximum, it was demonstrated that compound shows as single
Crystal phase, and inner layer space is gradually reduced with the increase of polyacid inlet.Intercalated compound and TCPP and P5W30Mixing it is molten
Liquid all shows anti-saturated absorption and self-defocusing property.But in TCPP and P5W30It interacts between the two in solution very weak, and
In intercalated compound, with P5W30The increase of content is so that the nonlinear response of TCPP gradually increases, as the P of addition5W30With
The mass ratio of the material of TCPP reach x/y=25.34/35 i.e. the intercalated compound of embodiment 12 when, three ranks of intercalated compound are non-
Linear response reaches maximum, and reason may can promote the TCPP and P under excitation state for the interlayer environment of hydrotalcite5W30Between electronics
And energy transmission.
It is that above-mentioned preferred embodiment should be regarded as application scheme embodiment for example, all with application scheme thunder
Same, approximate or technology deduction, replacement, improvement for making based on this etc., are regarded as the protection scope of this patent.
Claims (3)
1. a kind of optical material, which is characterized in that for by TCPP and Preyssler type polyoxometallate P5W30Intercalation enters altogether
Mg2Al-NO3Product (P obtained in hydrotalcite5W30)x-(TCPP)y/Mg2Al is total to intercalated compound, and the TCPP is four (right
Carboxyl phenyl) porphyrin, the P5W30For K12.5Na1.5[NaP5W30O110]·15H2O, the Mg2Al-NO3For nitrate anion magnesium
Aluminum hydrotalcite；Wherein, x represents P in product5W30Substance amount, y represents the amount of the substance of TCPP in product, and x/y represents product
Middle P5W30With the mass ratio of the material of TCPP；X/y=0~30/35.
2. optical material according to claim 1, which is characterized in that the x/y=25.34/35.
3. a kind of preparation method of optical material of any of claims 1 or 2, which is characterized in that include the following steps：
The preparation of S1.TCPP
P formylbenzoic acid 16g is dissolved in 500ml propionic acid, heating reaches reflux, and 7.40mL pyrroles is added dropwise, keeps back
Flow 1h；After the reaction was completed, it filters while hot, obtained solid first uses 160mLCH2Cl2It rinses, again with the flushing of 40mL tetrahydrofuran, it is dry
Gained precipitating, is recrystallized, product is purple powder in the mixed liquor of methanol and methylene chloride；
S2.P5W30Preparation
In 30mLH2The Disodium tungstate (Na2WO4) dihydrate of 33g is dissolved in O, and the phosphoric acid of 26.5ml is added thereto and is stirred evenly, gained is molten
Liquid moves into 100ml reaction kettle, reacts for 24 hours at 120 DEG C, reaction kettle is down to room temperature after the completion, gained mixture is moved to burning
In cup, 15mL deionized water and 10g potassium chloride being added thereto, is filtered under diminished pressure, obtained solid is rushed with 30mL 2M potassium acetate solution
It washes, then with 30mL CH3OH is rinsed, and obtains crude product, is recrystallized after crude product is dried with 200ml hot water, is obtained pure
Net product；
S3.Mg2Al-NO3The preparation and removing of hydrotalcite
Select constant pH coprecipitation Mg2Al-NO3Hydrotalcite：5.1g magnesium nitrate hexahydrate is added into 30mL deionized water
With 3.7g ANN aluminium nitrate nonahydrate；4g NaOH is dissolved in 50mL deionized water, precipitating reagent is made；Under nitrogen protection, to 25mL
It is pre-adjusted in the mixed solution for being slowly added to magnesium nitrate and aluminum nitrate in the deionized water of pH to 9.5, in the feelings being vigorously stirred
So that pH is maintained at 9.5 under condition, after dripping off, is warming up to 70 DEG C and continues to stir 60min, for 24 hours, mixture is centrifuged for heat preservation, is removed
Then supernatant liquid, obtained solid are dried in vacuo for 24 hours with a small amount of hot water injection；By gained 2.0g Mg2Al-NO3Neatly stone mill
It is broken；
Remove Mg2Al-NO3When hydrotalcite, the above-mentioned hydrotalcite of 0.4g is added into 400ml formamide under nitrogen protection and continues
Stirring two days, is prepared Mg2Al-NO3Hydrotalcite colloid；
S4. the preparation of intercalated compound powder and mixed solution
It is put into TCPP into 50ml water, the sodium hydroxide solution of 1M is added until TCPP is completely dissolved, pH=7.8-8.2, then plus
Enter P5W30, then under nitrogen protection, it is slowly added to the Mg that 20mL has been removed thereto2Al-NO3Colloid, stirring 20min are laggard
Row centrifugation, after centrifugation solid with hot water wash three times, in 80 DEG C of dry 48h, P5W30With the mass ratio of the material of TCPP be x/y=0~
30/35, by adjusting different the mass ratio of the materiaies, obtain different P5W30(the P of/TCPP ratio5W30)x-(TCPP)y/Mg2Al is total
Intercalated compound powder；
By the different P5W30(the P of/TCPP ratio5W30)x-(TCPP)y/Mg2Al is total to intercalated compound powder deionized water
Dissolution, obtains corresponding P5W30The intercalated compound mixed solution of/TCPP the mass ratio of the material, the i.e. optical material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530621A (en) * | 2009-03-18 | 2009-09-16 | 北京化工大学 | Oxidation resisting dipeptide medicament intercalated houghite and preparation method thereof |
| CN107224587A (en) * | 2017-06-28 | 2017-10-03 | 福州大学 | A kind of protoporphyrin zinc-aluminum hydrotalcite compound and its preparation method and application |
| CN107367884A (en) * | 2016-05-13 | 2017-11-21 | 北京化工大学 | A kind of polyacid-hydrotalcite third-order nonlinear optical film and preparation method thereof |
-
2018
- 2018-07-20 CN CN201810809188.2A patent/CN108873557A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530621A (en) * | 2009-03-18 | 2009-09-16 | 北京化工大学 | Oxidation resisting dipeptide medicament intercalated houghite and preparation method thereof |
| CN107367884A (en) * | 2016-05-13 | 2017-11-21 | 北京化工大学 | A kind of polyacid-hydrotalcite third-order nonlinear optical film and preparation method thereof |
| CN107224587A (en) * | 2017-06-28 | 2017-10-03 | 福州大学 | A kind of protoporphyrin zinc-aluminum hydrotalcite compound and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 李佳奇: "几种卟啉—多酸杂化材料的制备及其三阶非线性光学性质的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110180592A (en) * | 2019-06-27 | 2019-08-30 | 华侨大学 | A kind of preparation method of the catalyst for carbon dioxide hydrogenation reaction |
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