CN102702740B - Graphene/poly Schiff base polymer composite material and preparation method and application thereof - Google Patents
Graphene/poly Schiff base polymer composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a graphene/poly Schiff base polymer composite material and a preparation method and application thereof, and relates to a poly Schiff base composite material and a preparation method and application thereof. A structural formula of the graphene/poly Schiff base polymer composite material is shown in the specification. The preparation method comprises the following steps of: adding a poly Schiff base, graphene and sarcosine into anhydrous N,N'-dimethylformamide, performing ultrasonic processing, heating to the temperature of between 149 and 156 DEG C under the protection of N2, performing reflux and stirring for 4 to 10 days, reacting, filtering, washing and drying to obtain the graphene/poly Schiff base polymer composite material. The graphene/poly Schiff base polymer composite material can be used as a photoelectric material, and also can be used for detecting sensor devices, electrochromic display devices, acidichromic devices and photochromic devices.
Description
Technical field
The present invention relates to poly-schiff bases matrix material and its preparation method and application.
Background technology
The poly-schiff bases of aromaticity conjugation has optical nonlinearity, electrochromism, changing color resulting from acid, photochromic shape is, schiff base polymer has good mechanical property, thermostability and electron conduction, nonlinear optical property and many other performances simultaneously, is expected to be used in the interest that has caused many scholars in optical storage, light memory, optics computing, the lasing safety of light amplitude limit.But still there is poorly conductive in existing poly-schiff bases, and the slow and lower problem of efficient of variable color speed remains further research raising.
Summary of the invention
The present invention is the slow and lower problem of efficient of the poorly conductive that will solve existing poly-schiff bases, variable color speed, and Graphene/poly-schiff base polymer matrix material and its preparation method and application is provided.
The structural representation of Graphene of the present invention/poly-schiff base polymer matrix material is:
Graphene of the present invention/poly-schiff base polymer composite manufacture method is carried out according to the following steps:
One, adopt the Hummers method that graphite is made graphite oxide;
Two, again graphite oxide is reduced into Graphene with hydrazine hydrate;
Three, take by weighing Graphene and the sarkosine of poly-schiff bases, step 2 preparation and join anhydrous N, in N '-dimethyl formamide, supersound process 20min～30min is then at N
2Protection is lower, is warming up to 149～156 ℃ of return stirrings 4～10 days, and reaction finishes to filter, and the solid formation that obtains is clean with methanol wash, and then to be placed on temperature be 60～70 ℃ and use N
2Dry dry 10h～48h in the baking oven of protection obtains Graphene/poly-schiff base polymer matrix material;
Wherein the mass ratio of Graphene and poly-schiff bases is (0.5～1) in the step 3: 1, the mass ratio of sarkosine and poly-schiff bases is 1: (3～5), quality and the N of poly-schiff bases, the ratio of the volume of N '-dimethyl formamide is 1g: (20～50) mL.
The concrete steps that adopt the Hummers method that graphite is made graphite oxide in the step 1 are:
A, to take by weighing mass percentage concentration respectively be 98% the vitriol oil, Graphite Powder 99, SODIUMNITRATE, potassium permanganate and distilled water, and wherein Graphite Powder 99 quality and mass percentage concentration are that the ratio of the volume of 98% the vitriol oil is 1g: the mass ratio of (20～50) mL, Graphite Powder 99 and SODIUMNITRATE is 1: the mass ratio of (0.2～1.5), Graphite Powder 99 and potassium permanganate is 1: the quality of (4～7), Graphite Powder 99 is 1g with the ratio of distilled water volume: (20～30) mL;
B, Graphite Powder 99 and SODIUMNITRATE that step 1 is taken by weighing mix, and obtain mixture; The mass percentage concentration that step 1 is taken by weighing is that 98% the vitriol oil adds in the reaction vessel, again reaction vessel is placed in the ice-water bath, under agitation condition, mixture is joined in the reaction vessel, the potassium permanganate that again step 1 is taken by weighing divides and joins in the reaction vessel for 5～6 times, the control temperature of reaction is no more than 10～15 ℃, stirring reaction 2～4h; Then be warming up to 35 ℃～40 ℃, continue to stir 3h;
C, the distilled water that step 1 is taken by weighing add in the reaction vessel, continue to stir 30min～40min;
D, add hydrogen peroxide to the color of the solution in the reaction vessel and become by red-purple till the glassy yellow;
E, with the solidliquid mixture centrifugation in the reaction vessel, be 1mol/L HCl solution washing with concentration first with the solid formation that obtains again, again with deionized water wash till the sulfate radical-free, be dry 1h～10 day in 60～70 ℃ the vacuum drying oven in temperature again, obtain graphite oxide.
Graphite oxide is as follows with the concrete steps that hydrazine hydrate is reduced into Graphene in the step 2:
A, take by weighing graphite oxide, water and hydrazine hydrate, wherein the quality of graphite oxide is 1g with the ratio of the volume of water: the quality of (1000～1500) L, graphite oxide is 1g with the ratio of the volume of hydrazine hydrate: (10～30) mL;
B, the graphite oxide that step 1 is taken by weighing join in the water that step 1 takes by weighing, and obtain suspension, are ultra-sonic dispersion 1～5h under the condition of 500W again at power with suspension, obtain stable dispersion liquid;
C, the stable dispersion liquid that step B is obtained are warming up to 70～80 ℃, dropwise add hydrazine hydrate, after dropwising, be to stir 10h～36h under 80～90 ℃ the condition in temperature, then filter, the solid formation that obtains first with methanol wash, wash with water, is placed on temperature and is in 60～70 ℃ the vacuum drying oven dry 1～5 day more again, obtain Graphene.
The structural formula of the poly-schiff bases in the step 3 is:
The application of Graphene of the present invention/poly-schiff base polymer matrix material is the application as photoelectric material and detecting sensor part.
The application of Graphene of the present invention/poly-schiff base polymer matrix material is the application in making electrochromic display device.
The application of Graphene of the present invention/poly-schiff base polymer matrix material is the application in making the changing color resulting from acid device.
The application of Graphene of the present invention/poly-schiff base polymer matrix material is the application in making photochromic device.
Graphene of the present invention/poly-schiff base polymer matrix material be with sarkosine as intermediate, connect respectively poly-schiff bases and Graphene at the two ends of intermediate, Graphene and poly-schiff base polymer are combined with each other.Because the large π key on Graphene surface, this is so that Graphene is difficult to dispersion and dissolving in all kinds of SOLVENTS, the Graphene of structural integrity is the two dimensional crystal that combines by not containing any labile bond benzene six-ring, chemical stability is high, its surface is inert condition, easily produce and assemble, make it have not dissolving and be difficult to operate the control characteristics in all kinds of SOLVENTS, black alkene of the present invention/poly-schiff base polymer matrix material is that Graphene and the poly-schiff bases of aromaticity conjugation are carried out grafting, the characteristic that not only has the poly-schiff bases of Graphene and aromaticity conjugation, synergy is also arranged, multi-functional compound effect, the matrix material that obtains can dissolve in most organic solvents, can do support of the catalyst, have the third-order non-linear feature, also have good detection performance; Chemical bonding (carbon-to-carbon coupling) by Graphene and poly-schiff bases in Graphene/poly-schiff base polymer matrix material, form in the molecule or intermolecular flow of charge, widen spectral range, increase again the electroconductibility of system simultaneously, improve variable color speed and efficient.The Graphene of the present invention preparation/poly-schiff base polymer matrix material can anti-400 ℃ high temperature, has good resistance to elevated temperatures, is adapted at using in the device.Compare from the pure poly-schiff bases of equal in quality and the cyclic voltammetric spectrogram of Graphene/poly-schiff bases mixture, the electric current of knowing Graphene/poly-schiff bases mixture is all high than corresponding pure poly-schiff bases, illustrate to add that the electroconductibility of mixture strengthens behind the Graphene, improved the electroconductibility of polymkeric substance.Graphene of the present invention/poly-schiff base polymer matrix material can be used in the organic electroluminescence device, can improve the hole and inject density, thereby improve the luminescent properties of polymer electroluminescent device; Also have significant electrochromism, changing color resulting from acid, photochromic shape is, can be used for indicating meter and soda acid sensor, possesses simultaneously good thermostability.
Description of drawings
Fig. 1 is the stereoscan photograph of testing the Graphene that obtains once step 2;
Fig. 2 tests a Graphene for preparing/poly-schiff base polymer matrix material stereoscan photograph;
Fig. 3 is the infrared spectrogram of testing a Graphene for preparing/poly-schiff base polymer matrix material;
Fig. 4 is the Raman spectrogram of testing a Graphene for preparing/poly-schiff base polymer matrix material;
Fig. 5 is the thermogravimetric curve figure that tests a Graphene for preparing/poly-schiff base polymer matrix material;
Fig. 6 is that the Graphene/poly-schiff base polymer matrix material of test one preparation, pure Graphene, blank conductive glass, pure poly-schiff bases are to the cyclic voltammetry curve figure of the detection of TNT, wherein among the figure " ▲-" expression is that pure Graphene is to the cyclic voltammetry curve of the detection of TNT, " ■-" expression be blank conductive glass to the cyclic voltammetry curve of the detection of TNT, " ●-" expression is that pure poly-schiff bases is to the cyclic voltammetry curve of the detection of TNT;
Expression be that the Graphene that obtains through step 3/poly-schiff base polymer matrix material is to the cyclic voltammetry curve of the detection of TNT;
Fig. 7 is ultraviolet-visible absorption spectroscopy and the fluorescence spectrum figure that tests a Graphene for preparing/poly-schiff base polymer matrix material;
Fig. 8 be in the test one with Graphene/gather the ultraviolet-visible absorption spectroscopy figure of electrochromic display device under 0V～1.6V voltage that the schiff base polymer matrix material is made, the direction indication voltage of " → " indication increases gradually among the figure;
Fig. 9 be in the test one with the ultraviolet-visible absorption spectroscopy of changing color resulting from acid indicating meter after passing into the concentrated hydrochloric acid gas of 1000～10000ppm that Graphene/poly-schiff base polymer matrix material is made reach after passing into ammonia again ultraviolet-visible absorption spectroscopy figure, wherein the direction indication of " → " indication passes into hydrochloric acid content increases gradually; A represents to pass into after passing into concentrated hydrochloric acid gas the ultraviolet-visible absorption spectroscopy of ammonia again;
Figure 10 is that the chloroformic solution of the Graphene/poly-schiff base polymer matrix material of test one preparation adds the ultraviolet-visible absorption spectroscopy of hydrazine hydrate again after the ultraviolet-visible absorption spectroscopy after the 365nm UV-irradiation and illumination, and the direction indication light application time of " → " indication increases gradually among the figure; B represents to add after the illumination ultraviolet-visible absorption spectroscopy of hydrazine hydrate again.
Embodiment
Embodiment one: the structural formula of the Graphene of present embodiment/poly-schiff base polymer matrix material is:
The black alkene of present embodiment/poly-schiff base polymer matrix material is that Graphene and the poly-schiff bases of aromaticity conjugation are carried out grafting, the characteristic that not only has the poly-schiff bases of Graphene and aromaticity conjugation, synergy, multi-functional compound effect are also arranged, the matrix material that obtains can dissolve in most organic solvents, can do support of the catalyst, have the third-order non-linear feature, also have good detection performance; Chemical bonding (carbon-to-carbon coupling) by Graphene and poly-schiff bases in Graphene/poly-schiff base polymer matrix material, form in the molecule or intermolecular flow of charge, widen spectral range, increase again simultaneously the electroconductibility of system, improve variable color speed and efficient, improved simultaneously the electroconductibility of material.
Embodiment two: embodiment one described Graphene/poly-schiff base polymer composite manufacture method is carried out according to the following steps:
One, adopt the Hummers method that graphite is made graphite oxide;
Two, again graphite oxide is reduced into Graphene with hydrazine hydrate;
Three, take by weighing Graphene and the sarkosine of poly-schiff bases, step 2 preparation and join anhydrous N, in N '-dimethyl formamide, supersound process 20min～30min is then at N
2Protection is lower, is warming up to 149～156 ℃ of return stirrings 4～10 days, and reaction finishes to filter, and the solid formation that obtains is clean with methanol wash, and then to be placed on temperature be 60～70 ℃ and use N
2Dry dry 10h～48h in the baking oven of protection obtains Graphene/poly-schiff base polymer matrix material;
Wherein the mass ratio of Graphene and poly-schiff bases is (0.5～1) in the step 3: 1, the mass ratio of sarkosine and poly-schiff bases is 1: (3～5), quality and the N of poly-schiff bases, the ratio of the volume of N '-dimethyl formamide is 1g: (20～50) mL.
The black alkene of present embodiment preparation/poly-schiff base polymer matrix material is that Graphene and the poly-schiff bases of aromaticity conjugation are carried out grafting, the characteristic that not only has the poly-schiff bases of Graphene and aromaticity conjugation, synergy, multi-functional compound effect are also arranged, the matrix material that obtains can dissolve in most organic solvents, can do support of the catalyst, have the third-order non-linear feature, also have good detection performance; Chemical bonding (carbon-to-carbon coupling) by Graphene and poly-schiff bases in Graphene/poly-schiff base polymer matrix material, form in the molecule or intermolecular flow of charge, widen spectral range, increase again simultaneously the electroconductibility of system, improve variable color speed and efficient, improved simultaneously the electroconductibility of material.
Embodiment three: what present embodiment and implementation two were different is: the concrete steps that adopt the Hummers method that graphite is made graphite oxide in the step 1 are:
A, to take by weighing mass percentage concentration respectively be 98% the vitriol oil, Graphite Powder 99, SODIUMNITRATE, potassium permanganate and distilled water, and wherein Graphite Powder 99 quality and mass percentage concentration are that the ratio of the volume of 98% the vitriol oil is 1g: the mass ratio of (20～50) mL, Graphite Powder 99 and SODIUMNITRATE is 1: the mass ratio of (0.2～1.5), Graphite Powder 99 and potassium permanganate is 1: the quality of (4～7), Graphite Powder 99 is 1g with the ratio of distilled water volume: (20～30) mL;
B, Graphite Powder 99 and SODIUMNITRATE that step 1 is taken by weighing mix, and obtain mixture; The mass percentage concentration that step 1 is taken by weighing is that 98% the vitriol oil adds in the reaction vessel, again reaction vessel is placed in the ice-water bath, under agitation condition, mixture is joined in the reaction vessel, the potassium permanganate that again step 1 is taken by weighing divides and joins in the reaction vessel for 5～6 times, the control temperature of reaction is no more than 10～15 ℃, stirring reaction 2～4h; Then be warming up to 35 ℃～40 ℃, continue to stir 3h;
C, the distilled water that step 1 is taken by weighing add in the reaction vessel, continue to stir 30min～40min;
D, add hydrogen peroxide to the color of the solution in the reaction vessel and become by red-purple till the glassy yellow;
E, with the solidliquid mixture centrifugation in the reaction vessel, be 1mol/L HCl solution washing with concentration first with the solid formation that obtains again, again with deionized water wash till the sulfate radical-free, be dry 1h～10 day in 60～70 ℃ the vacuum drying oven in temperature again, obtain graphite oxide.Other is identical with embodiment two.
Embodiment four: what present embodiment was different from implementation two or three is: graphite oxide is as follows with the concrete steps that hydrazine hydrate is reduced into Graphene in the step 2:
A, take by weighing graphite oxide, water and hydrazine hydrate, wherein the quality of graphite oxide is 1g with the ratio of the volume of water: the quality of (1000～1500) L, graphite oxide is 1g with the ratio of the volume of hydrazine hydrate: (10～30) mL;
B, the graphite oxide that step 1 is taken by weighing join in the water that step 1 takes by weighing, and obtain suspension, are ultra-sonic dispersion 1～5h under the condition of 500W again at power with suspension, obtain stable dispersion liquid;
C, the stable dispersion liquid that step B is obtained are warming up to 70～80 ℃, dropwise add hydrazine hydrate, after dropwising, be to stir 10h～36h under 80～90 ℃ the condition in temperature, then filter, the solid formation that obtains first with methanol wash, wash with water, is placed on temperature and is in 60～70 ℃ the vacuum drying oven dry 1～5 day more again, obtain Graphene.Other is identical with embodiment two or three.
Embodiment five: what present embodiment was different from one of implementation two to four is: the structural formula of the poly-schiff bases in the step 3 is:
Embodiment six: the application of embodiment one described Graphene/poly-schiff base polymer matrix material is that it is as the application of photoelectric material.
Embodiment seven: the application of embodiment one described Graphene/poly-schiff base polymer matrix material is its application in the detecting sensor part.
Embodiment eight: the application of embodiment one described Graphene/poly-schiff base polymer matrix material is its application in electrochromic display device.
Embodiment nine: the application of embodiment one described Graphene/poly-schiff base polymer matrix material is its application in the changing color resulting from acid device.
Embodiment ten: the application of embodiment one described Graphene/poly-schiff base polymer matrix material is its application in photochromic device.
With following verification experimental verification beneficial effect of the present invention:
Test one: Graphene of the present invention/poly-schiff base polymer composite manufacture method is carried out according to the following steps:
One, adopt the Hummers method that graphite is made graphite oxide: A, to take by weighing the 50mL mass percentage concentration respectively be 98% the vitriol oil, 2.0099g Graphite Powder 99,1.0629g SODIUMNITRATE, 6.023g potassium permanganate and 20mL distilled water; B, Graphite Powder 99 and SODIUMNITRATE that step 1 is taken by weighing mix, and obtain mixture; The mass percentage concentration that step 1 is taken by weighing is that 98% the vitriol oil adds in the reaction vessel, again reaction vessel is placed in the ice-water bath, under agitation condition, mixture is joined in the reaction vessel, the potassium permanganate that again step 1 is taken by weighing divides and joins in the reaction vessel for 6 times, the control temperature of reaction is no more than 15 ℃, stirring reaction 2h; Then be warming up to 35 ℃, continue to stir 3h; C, the distilled water that step 1 is taken by weighing add in the reaction vessel, continue to stir 30min; D, add hydrogen peroxide to the color of the solution in the reaction vessel and become by red-purple till the glassy yellow; E, be centrifugation 8min under the condition of 6000rmp at rotating speed with the solidliquid mixture in the reaction vessel, be 1mol/L HCl solution washing with 150mL concentration first with the solid formation that obtains again, again with deionized water wash till the sulfate radical-free, be dry 24h in 60 ℃ the vacuum drying oven in temperature again, obtain the 2.0338g graphite oxide;
Two, again graphite oxide is reduced into Graphene with hydrazine hydrate: A, take by weighing 300mg graphite oxide, 300g water and 6mL hydrazine hydrate; B, the graphite oxide that step 1 is taken by weighing join in the water that step 1 takes by weighing, and obtain suspension, are ultra-sonic dispersion 5h under 500 the condition again at power with suspension, obtain stable dispersion liquid; C, the stable dispersion liquid that step B is obtained are warming up to 80 ℃, dropwise add hydrazine hydrate, after dropwising, be to stir 24h under 80 ℃ the condition in temperature, then filter, the solid formation that obtains first with twice of methanol wash, wash with water 3 times, is placed on temperature and is dry 24h in 60 ℃ the vacuum drying oven more again, obtain the 0.1732g Graphene;
Three, take by weighing 0.1012g and gather Graphene and the 0.0214g sarkosine of schiff bases, the preparation of 0.06g step 2 and join the anhydrous N of 50mL, in N '-dimethyl formamide, supersound process 20min is then at N
2Protection is lower, is warming up to 153 ℃ of return stirrings 4 days, and reaction finishes to filter, and with methanol wash 3 times, then to be placed on temperature be 60 ℃ and use N with the solid formation that obtains
2Dry dry 24h in the baking oven of protection obtains 0.047g Graphene/poly-schiff base polymer matrix material.
The structural formula of the described poly-schiff bases of step 3 is in this test:
, n wherein is 1～100 integer.
The structural representation of the Graphene that this test obtains through step 3/poly-schiff base polymer matrix material is:
The composition principle of Graphene of the present invention/poly-schiff base polymer matrix material is as follows:
The Graphene stereoscan photograph that this test obtains through step 2 as shown in Figure 1, the Graphene that this test obtains through step 3/poly-schiff base polymer matrix material stereoscan photograph as shown in Figure 2, comparison diagram 1 and Fig. 2, there is fold on the surface that can find out pure Graphene, and there is one deck coverture on the surface of Graphene/poly-schiff base polymer matrix material, illustrates that poly-schiff bases successfully is grafted on the Graphene.
The infrared spectrogram of the Graphene that this test obtains through step 3/poly-schiff base polymer matrix material as shown in Figure 3, as can be seen from the figure, 1497cm
-1Belong to the stretching vibration of O-H, 1600cm
-1, 1500cm
-1There are phenyl ring stretching vibration characteristic peak, 1626cm in the place
-1The place belongs to C=N peak on the poly-schiff bases, 1671cm
-1Weakening of C=O peak, place illustrates in the successful grafting of Graphene and poly-schiff bases.
The Raman spectrogram of the Graphene that this test obtains through step 3/poly-schiff base polymer matrix material as shown in Figure 4, as can be seen from the figure, 1351cm
-1The D peak that belongs to Graphene, 1582cm
-1The E peak that belongs to Graphene.
This test is through Graphene that step 3 obtains/the poly-thermogravimetric curve of schiff base polymer matrix material under nitrogen atmosphere as shown in Figure 5, as can be seen from Figure 5, the Graphene of this test preparation/poly-schiff base polymer matrix material is under nitrogen atmosphere, be 400 ℃ in temperature and locate weightless 10%, locate weightless 40% at 600 ℃, therefore, Graphene/poly-schiff base polymer matrix material has good resistance to elevated temperatures, is adapted at using in the device.
To gather schiff bases
(wherein n=20～60), Graphene, and the Graphene of this test preparation/poly-schiff base polymer matrix material is dissolved in the chloroform, all be mixed with the solution that concentration is 3.75g/L, getting respectively mentioned solution is coated on the ito glass, again take the conductive glass of filming as working electrode, take platinum filament as to electrode, take silver-silver chloride electrode as reference electrode, the acetonitrile solution that dewaters take concentration as the 0.1mlo/L lithium perchlorate is as ionogen, carry out the interactional cyclic voltammetry of above-mentioned substance and TNT, the cyclic voltammogram that obtains as shown in Figure 6, wherein " ▲-" what represent is that Graphene is to the cyclic voltammetry curve of the detection of TNT, " ■-" expression be blank ITO conductive glass to the cyclic voltammetry curve of the detection of TNT, " ●-" expression is that poly-schiff bases is to the cyclic voltammetry curve of the detection of TNT;
Expression be the Graphene that obtains through step 3 of this test/gather the schiff base polymer matrix material to the cyclic voltammetry curve of the detection of TNT.As seen, blank ITO is straight line, does not have the redox peak among the figure; Poly-schiff bases and TNT interact two oxidation peak (0.75v, 1.10v) and three reduction peak (0.72v, 0.56v, 0.88v) are arranged; Graphene and TNT interact a pair of redox peak, oxidation peak (0.37v), and reduction peak is (0.79v); Graphene/poly-schiff base polymer matrix material combines the common feature of Graphene and poly-schiff bases, two pairs of oxidation peak (1.03v, 1.55v) and three reduction peak (0.59v, 0.61v, 0.92v) are arranged, and the intensity at peak is stronger.The interaction that matrix material and TNT are described is stronger.And can find out also that from Fig. 6 the electric current of Graphene/poly-schiff base polymer matrix material is all high than corresponding pure poly-schiff bases, and the electroconductibility enhancing that adds the mixture behind the Graphene be described, improved the electroconductibility of polymkeric substance.
The ultraviolet-visible absorption spectroscopy of the Graphene that this test obtains through step 3/poly-schiff base polymer matrix material and fluorescence spectrum figure as shown in Figure 7, wherein " ■-" is the ultraviolet-visible absorption spectroscopy curve, " ▲-" is fluorescent spectrum curve; As can be seen from the figure, please replenish.At 334cm
-1Strong ultraviolet absorption peak is arranged, at 626cm
-1Strong fluorescent absorption peak is arranged.
The Graphene of this test preparation/application of poly-schiff base polymer matrix material in making electrochromic display device: the 0.05g Graphene of this test preparation/gather schiff base polymer matrix material is dissolved in obtains matrix material solution in the 1mL chloroform, again matrix material solution is spin-coated on the conductive glass, the conductive glass that obtains filming, take the conductive glass of filming as working electrode, platinum filament is to electrode, the silver-silver chloride electrode reference electrode, take acetonitrile as solution, lithium perchlorate is that ionogen is made transparent electrochromic display device.The test electrochromic display device is under 0V～1.6V voltage (0,0.7,0.9,1.0V, 1,1V, 1.2,1.3,1.4,1.5, ultraviolet-visible absorption spectroscopy figure 1.6V) as shown in Figure 8, the direction of " → " indication is that voltage increases gradually among the figure, as can be seen from Figure 8, along with the increase of voltage, 328,399,434, the absorption peak at 1224nm place all strengthens, and the absorption peak at 381nm place descends and blue shift 12nm left; New absorption peak appears in the 526nm place; 458 and 588nm two iso-electric points appear, illustrate three kinds of colour-change have occured in the electrochromic process.
The Graphene of this test preparation/application of poly-schiff base polymer matrix material in making the changing color resulting from acid device: the 0.05g Graphene of this test preparation/gather schiff base polymer matrix material is dissolved in obtains matrix material solution in the 1mL chloroform, again matrix material solution is spin-coated on the conductive glass, the conductive glass that obtains filming, take the conductive glass of filming as working electrode, platinum filament is to electrode, silver-silver chloride electrode is reference electrode, take acetonitrile as solution, lithium perchlorate is that ionogen is made the changing color resulting from acid device, the ultraviolet-visible absorption spectroscopy figure of test changing color resulting from acid display device after passing into the concentrated hydrochloric acid gas of 1000～10000ppm as shown in Figure 9, the direction of " → " indication increases gradually for passing into hydrochloric acid content, and a among Fig. 9 represents to pass into after passing into concentrated hydrochloric acid gas the ultraviolet-visible absorption spectroscopy of ammonia again.As can be seen from Figure 9, passing into concentrated hydrochloric acid gas namely has obvious absorption peak at the 637nm place afterwards, absorbs orange light, and Graphene/poly-schiff base polymer is shown as turquoise; This is that this ion is turquoise owing to having formed the acid positively charged ion of polymkeric substance after adding hydrochloric acid.And along with the increase that is blown into hydrochloric acid content, the peak at 480nm place (the absorption peak position of Graphene when not adding acid/poly-schiff base polymer) reduces gradually, the rising gradually of the peak at 637 places, and the color of the solution becomes blueness by yellow.After being blown into ammonia again, be blown into ammonia after solution begin again to occur absorption peak at 480nm.Illustrate in the polymkeric substance changing color resulting from acid phenomenon to have occured after adding acid gas, be blown into ammonia, solution colour reverts to virgin state again, illustrates that the changing color resulting from acid of the Graphene of this test/poly-schiff base polymer matrix material has reversibility.
The Graphene of this test preparation/application of poly-schiff base polymer matrix material in making photochromic device: the solution after the Graphene that this test is prepared/poly-schiff base polymer matrix material dissolves with chloroform, then solution is carried out the 365nm UV-irradiation, light application time is followed successively by 0s, 15s, 45s, 75s, 105s, 130s, 175s, 200s, then the solution after the illumination is carried out the ultraviolet-visible absorption spectroscopy test, the ultraviolet-visible absorption spectroscopy that obtains as shown in Figure 10, the direction of " → " indication is the ultraviolet-visible absorption spectroscopy of the solution that increases gradually of light application time among Figure 10, and the b among Figure 10 represents to add after the illumination ultraviolet-visible absorption spectroscopy of hydrazine hydrate again.Along with the increase of light application time, the ultraviolet and visible absorption peak of Graphene/poly-schiff base polymer matrix material is moved to right to 637nm by 483nm place, absorption be blue-greenish colour, and Graphene/gather the schiff base polymer matrix material to be shown as orange-yellow.Absorption peak appears again in the 483nm place after adding hydrazine hydrate, and the absorption peak at 637nm place disappears.Photochromic sensitivity, response is fast, and the change in displacement of obvious absorption peak is arranged during 365nm UV-irradiation 15s.
Claims (9)
1. Graphene/poly-schiff base polymer matrix material is characterized in that the structural formula expression of Graphene/poly-schiff base polymer matrix material is:
Described Graphene/poly-schiff base polymer composite manufacture method is as follows:
One, adopt the Hummers method that graphite is made graphite oxide;
Two, again graphite oxide is reduced into Graphene with hydrazine hydrate;
Three, take by weighing Graphene and the sarkosine of poly-schiff bases, step 2 preparation and join anhydrous N, in N '-dimethyl formamide, supersound process 20min～30min is then at N
2Protection is lower, is warming up to 149～156 ℃ of return stirrings 4～10 days, and reaction finishes to filter, and the solid formation that obtains is clean with methanol wash, and then to be placed on temperature be 60～70 ℃ and use N
2Dry 10h～48h in the baking oven of protection obtains Graphene/poly-schiff base polymer matrix material;
Wherein the mass ratio of Graphene and poly-schiff bases is (0.5～1) in the step 3: 1, the mass ratio of sarkosine and poly-schiff bases is 1:(3～5), quality and the N of poly-schiff bases, the ratio of the volume of N '-dimethyl formamide is 1g:(20～50) mL.
2. Graphene according to claim 1/poly-schiff base polymer composite manufacture method is characterized in that the concrete steps that adopt the Hummers method that graphite is made graphite oxide in the step 1 are:
A, to take by weighing mass percentage concentration respectively be 98% the vitriol oil, Graphite Powder 99, SODIUMNITRATE, potassium permanganate and distilled water, and wherein Graphite Powder 99 quality and mass percentage concentration are that the ratio of the volume of 98% the vitriol oil is 1g:(20～50) mass ratio of mL, Graphite Powder 99 and SODIUMNITRATE is 1:(0.2～1.5), the mass ratio of Graphite Powder 99 and potassium permanganate is 1:(4～7), the quality of Graphite Powder 99 is 1g:(20～30 with the ratio of distilled water volume) mL;
B, Graphite Powder 99 and SODIUMNITRATE that step 1 is taken by weighing mix, and obtain mixture; The mass percentage concentration that step 1 is taken by weighing is that 98% the vitriol oil adds in the reaction vessel, again reaction vessel is placed in the ice-water bath, under agitation condition, mixture is joined in the reaction vessel, the potassium permanganate that again step 1 is taken by weighing divides and joins in the reaction vessel for 5～6 times, the control temperature of reaction is no more than 10～15 ℃, stirring reaction 2～4h; Then be warming up to 35 ℃～40 ℃, continue to stir 3h;
C, the distilled water that step 1 is taken by weighing add in the reaction vessel, continue to stir 30min～40min;
D, add hydrogen peroxide to the color of the solution in the reaction vessel and become by red-purple till the glassy yellow;
E, with the solidliquid mixture centrifugation in the reaction vessel, be 1mol/L HCl solution washing with concentration first with the solid formation that obtains again, again with deionized water wash till the sulfate radical-free, be dry 1h～10 day in 60～70 ℃ the vacuum drying oven in temperature again, obtain graphite oxide.
3. Graphene according to claim 1 and 2/poly-schiff base polymer composite manufacture method is characterized in that graphite oxide is as follows with the concrete steps that hydrazine hydrate is reduced into Graphene in the step 2:
A, take by weighing graphite oxide, water and hydrazine hydrate, wherein the quality of graphite oxide is 1g:(1000～1500 with the ratio of the volume of water) quality of L, graphite oxide is 1g:(10～30 with the ratio of the volume of hydrazine hydrate) mL;
B, the graphite oxide that step 1 is taken by weighing join in the water that step 1 takes by weighing, and obtain suspension, are ultra-sonic dispersion 1～5h under the condition of 500W again at power with suspension, obtain stable dispersion liquid;
C, the stable dispersion liquid that step B is obtained are warming up to 70～80 ℃, dropwise add hydrazine hydrate, after dropwising, be to stir 10h～36h under 80～90 ℃ the condition in temperature, then filter, the solid formation that obtains first with methanol wash, wash with water, is placed on temperature and is in 60～70 ℃ the vacuum drying oven dry 1～5 day more again, obtain Graphene.
4. Graphene according to claim 1 and 2/poly-schiff base polymer composite manufacture method is characterized in that the structural formula of the poly-schiff bases in the step 3 is:
5. the application of Graphene as claimed in claim 1/poly-schiff base polymer matrix material is characterized in that the application of Graphene/poly-schiff base polymer matrix material is that it is as the application of photoelectric material.
6. the application of Graphene as claimed in claim 1/poly-schiff base polymer matrix material is characterized in that the application of Graphene/poly-schiff base polymer matrix material is its application in the detecting sensor part.
7. the application of Graphene as claimed in claim 1/poly-schiff base polymer matrix material is characterized in that the application of Graphene/poly-schiff base polymer matrix material is its application in electrochromic display device.
8. the application of Graphene as claimed in claim 1/poly-schiff base polymer matrix material is characterized in that the application of Graphene/poly-schiff base polymer matrix material is its application in the changing color resulting from acid device.
9. the application of Graphene as claimed in claim 1/poly-schiff base polymer matrix material is characterized in that the application of Graphene/poly-schiff base polymer matrix material is its application in photochromic device.
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