CN104449692B - As lucigenin smectite composite material that scalable is luminous and its preparation method and application - Google Patents

Abstract

The invention discloses a method for preparing a glossy saponite composite material and the glossy saponite composite material prepared by the method. The preparation method is simple and easy, the preparation condition is mild, the operation is simple, the raw material is easily available, and the price is low. The production cost is low; the luster essence saponite composite material prepared by the method has stable performance, strong thermal stability, and significantly prolongs the fluorescence lifetime. Under the same luminous intensity and fluorescence lifetime requirements, the usage amount of the gloss essence can be reduced, thereby Save the cost of use.

Description

As glossy saponite composite material with adjustable luminescence and its preparation method and application

technical field

The invention relates to the field of luminescent materials, in particular to a glossy saponite composite material with adjustable luminescence and a preparation method thereof.

Background technique

After the matter is excited (such as rays, high-energy particles, electron beams or external electric fields, etc.), it will be in an excited state, and the energy in the excited state will be released in the form of light or heat. If the released energy is in the visible, ultraviolet or Near-infrared electromagnetic radiation, this process is called the luminescence process, and the substance that can realize the luminescence process is called the luminescent material.

Among the light-emitting materials, organic small molecule light-emitting materials occupy a considerable proportion. Compared with inorganic light-emitting materials, they have many incomparable advantages, such as: easy to purify, luminous brightness and color purity are also better than polymer materials, and their emission spectrum Wide coverage; can obtain luminescence in the visible spectrum range, especially the blue light that is difficult to obtain from inorganic materials; can be directly driven by DC low voltage of more than ten volts or even several volts, directly matching with integrated circuits; production of organic electroluminescent devices The process is simple, an ultra-thin flat panel display device can be made at low cost, and industrialization is easy.

However, small organic molecules are prone to concentration quenching effects, resulting in reduced luminous efficiency.

Lucigenin is used in luminescent materials. It has the characteristics of strong chemical modification, easy purification, wide source, wide selectivity and wide coverage of emission spectrum. It is a widely used organic small molecule luminescent material. It also has serious problems in solid state The concentration quenching problem of lucigenin, that is, when the concentration of lucigenin increases, its luminous efficiency, luminous intensity and fluorescence lifetime decrease, which seriously limits its use under solid-state conditions, and the luminous intensity of lucigenin with a small concentration cannot meet the needs.

Therefore, there is an urgent need for a material with a small concentration quenching effect, which can improve the luminous efficiency of lucigenin and prolong its fluorescence lifetime, and a preparation method thereof.

Contents of the invention

In order to solve the above problems, the present inventors have carried out intensive research, and found that: soapstone has a layered structure, and the interlayer distance of the soapstone can be controlled by controlling the silicon-aluminum ratio in the raw material when preparing the soapstone, and the combination of gloss essence and Composite the saponite in interlayer spacing, and the obtained composite material has significantly enhanced luminous intensity and significantly improved fluorescence lifetime compared with simple lucigen, thereby completing the present invention.

The purpose of the present invention is to provide the following aspects:

In the first aspect, a method for preparing glossy saponite composite material is characterized in that the method comprises the following steps:

(1) drying and pulverizing the soapstone, and preparing the lucigen essence into an aqueous solution of the lucigen essence;

(2) Add the saponite pulverized in step 1 into the lucigenin aqueous solution under stirring conditions, stir, and let stand;

(3) The product obtained in step 2 is heated and stirred, and aged;

(4) The product obtained in step 3 is separated, washed and dried.

In a second aspect, the present invention also provides the glossy saponite composite material prepared according to the above method, characterized in that,

The soapstone used is a saponite with a silica-alumina ratio of 3.90/0.10 to 2.50/1.50, preferably 3.74/0.26 to 2.80/1.20; and/or

In the obtained lucigenite saponite composite material, the intercalation amount of lucigenin is 0.15mmol/g-0.35mmol/g, preferably 0.16mmol/g-0.28mmol/g; and/or

According to the XRD spectrum, there is an absorption peak at a 2θ angle of about 4.2° to 6°; and/or

According to the fluorescence spectrum, it has an absorption peak at a wavelength of about 550nm.

In the third aspect, the present invention also provides the application of the above-mentioned glossy saponite composite material in organic light-emitting molecular devices, which has the advantages of high luminous intensity and strong stability.

Description of drawings

Fig. 1 a shows the XRD spectrogram of saponite raw material used in the embodiment 1～6, wherein,

Curve A represents the XRD spectrogram of the saponite raw material used in embodiment 1;

Curve B represents the XRD spectrogram of the saponite raw material used in embodiment 2;

Curve C represents the XRD spectrogram of the saponite raw material used in embodiment 3;

Curve D represents the XRD spectrogram of the saponite raw material used in embodiment 4;

Curve E represents the XRD spectrogram of the saponite raw material used in embodiment 5;

Curve F represents the XRD spectrogram of the saponite raw material used in embodiment 6;

Fig. 1b shows the XRD figure of the sample that embodiment 1～6 makes, wherein,

Curve A represents the XRD figure of the sample that embodiment 1 makes;

Curve B represents the XRD figure of the sample that embodiment 2 makes;

Curve C represents the XRD figure of the sample that embodiment 3 makes;

Curve D represents the XRD figure of the sample that embodiment 4 makes;

Curve E represents the XRD figure of the sample that embodiment 5 makes;

Curve F represents the XRD figure of the sample that embodiment 6 makes;

Fig. 2 shows that embodiment 1～6 makes the sample and the fluorescence spectrum of gloss essence, wherein,

Curve BNMA represents the fluorescence spectrum of the untreated lucigenin product;

Curve A represents the fluorescent spectrum of the sample that embodiment 1 makes;

Curve B represents the fluorescent spectrum of the sample that embodiment 2 makes;

Curve C represents the fluorescence spectrum of the sample obtained in Example 3;

Curve D represents the fluorescence spectrum of the sample that embodiment 4 makes;

Curve E represents the fluorescence spectrum of sample that embodiment 5 makes;

Curve F represents the fluorescence spectrum of the sample that embodiment 6 makes;

Fig. 3 shows the fluorescence time-resolved delay curves of samples and lucigenin prepared in Examples 1 to 6, wherein,

Curve BNMA represents the fluorescence time-resolved delay curve of the untreated lucigenin product;

Curve A represents the fluorescence time-resolved delay curve of the sample prepared in Example 1;

Curve B represents the fluorescence time-resolved delay curve of the sample prepared in Example 2;

Curve C represents the fluorescence time-resolved delay curve of the sample obtained in Example 3;

Curve D represents the fluorescence time-resolved delay curve of the sample obtained in Example 4;

Curve E represents the fluorescence time-resolved delay curve of the sample obtained in Example 5;

Curve F represents the fluorescence time-resolved delay curve of the sample obtained in Example 6;

Fig. 4a shows the fluorescence emission curves of the untreated lucigenin product at different temperatures, wherein,

Curve A represents the fluorescence emission curve at 25°C;

Curve B represents the fluorescence emission curve at 50°C;

Curve C represents the fluorescence emission curve at 75°C;

Figure 4b shows the fluorescence emission curves of the samples prepared in Example 6 at different temperatures, wherein,

Curve A represents the fluorescence emission curve at 25°C;

Curve B represents the fluorescence emission curve at 50°C;

Curve C represents the fluorescence emission curve at 75°C;

Curve D represents the fluorescence emission curve at 100°C;

Curve E represents the fluorescence emission curve at 150°C;

Curve F represents the fluorescence emission curve at 200°C;

Curve G represents the fluorescence emission curve at 300°C;

Figure 5a1 shows the energy band diagram of the untreated lucigenin product;

Figure 5a2 shows the density of states diagram for the untreated lucigenin product;

Fig. 5b1 shows the energy band diagram of the sample prepared in embodiment 6;

Fig. 5b2 shows the density of state figure of the sample that embodiment 6 makes;

Fig. 6 a shows the ²⁷ Al magic angle rotation method nuclear magnetic resonance spectrogram of the saponite raw material used in embodiments 1～6, wherein,

Curve A represents the used saponite raw material of embodiment 1 ²⁷ Al magic angle rotation method NMR spectrogram;

Curve B represents the used saponite raw material of embodiment 2 ⁷ Al magic angle rotation method NMR spectrogram;

Curve C represents the used saponite raw material of embodiment 3 ²⁷ Al magic angle rotation method NMR spectrogram;

Curve D represents the used saponite raw material of embodiment 4 ²⁷ Al magic angle rotation method NMR spectrogram;

Curve E represents the used saponite raw material of embodiment 5 ²⁷ Al magic angle rotation method NMR spectrogram;

Curve F represents the used saponite raw material of embodiment 6 ²⁷ Al magic angle rotation method NMR spectrogram;

Fig. 6 b shows the ²⁹ Si cross-polarized magic-angle rotation method nuclear magnetic resonance spectrogram of the saponite raw material used in Examples 1-6, wherein,

Curve A represents the ²⁹ Si cross-polarization magic-angle rotation method NMR spectrogram of the saponite raw material used in embodiment 1;

Curve B represents the ²⁹ Si cross-polarization magic-angle rotation method NMR spectrogram of the saponite raw material used in embodiment 2;

Curve C represents the ²⁹ Si cross-polarization magic-angle rotation method NMR spectrogram of the saponite raw material used in embodiment 3;

Curve D represents the used saponite raw material of embodiment 4 ^29Si cross-polarization magic-angle rotation method NMR spectrogram;

Curve E represents the used saponite raw material of embodiment 5 ²⁹ Si cross-polarization magic-angle rotation method NMR spectrogram;

Curve F represents the ²⁹ Si cross-polarized magic-angle rotation NMR spectrum of the saponite raw material used in Example 6.

detailed description

The following describes the present invention in detail, and the features and advantages of the present invention will become more clear and definite along with these descriptions.

The present invention is described in detail below.

According to a first aspect of the present invention, there is provided a method for preparing a glossy saponite composite material, the method comprising the following steps:

In step 1, the soapstone is dried and crushed; and the lucigen essence is prepared into an aqueous lucigen essence solution.

The present invention does not specifically limit to the source of soapstone, can be natural soapstone also can be artificially synthesized soapstone, it is preferred to be able to make glossy saponite composite material, and the present invention does not make the method for preparing soapstone Specifically defined, such as the method described in KAWIS, YAOYZ. Saponite catalysts with systematically varied Mg/Niratio: synthesis, characterization, and catalysis [J]. Micropor Mesopor Mater, 1999, 33 (1-3): 49-59.

When preparing saponite, the inventors found that the ratio of silicon to aluminum in the raw material is controlled to be 3.90/0.10 to 2.50/1.50, and the degree of compounding of the prepared saponite and glossinite is significantly increased, and the prepared glossinite saponite composite material Therefore, the present invention selects saponite with a silicon-aluminum ratio of 3.90/0.10 to 2.50/1.50, and preferably uses a saponite with a silicon-aluminum ratio of 3.74/0.26 to 2.80/1.20.

The soapstone is dried under the condition of 50°C to 80°C. The inventors found that when the drying temperature is higher than 80°C, the interlayer bound water in the soapstone will escape from the soapstone in the form of free water, thereby The interlayer structure of saponite is destroyed, therefore, the preferred drying temperature in the present invention is 55°C to 70°C, such as 60°C.

In the present invention, the drying time is not particularly limited, and the free water present in the soapstone is preferably removed, such as 1 to 5 hours, preferably 2 to 4 hours.

The inventors found that when the particle size of the saponite particles is micron, its dispersibility in the lucigenin aqueous solution is good, and further, it is fully compounded with the lucigenin. 80 μm, preferably 40 μm to 70 μm, more preferably 50 μm to 60 μm.

When the concentration of the lucigenin aqueous solution is greater than 1000mg/L, in addition to the lucigenin intercalation between the saponite layers, the excess lucigenin gathers on the outer surface of the smectite, resulting in the lucigenin-saponite composite material still having a concentration quenching effect and affecting The luminescent performance of composite material; when the concentration of lucigen essence aqueous solution is lower than 20mg/L, the amount of lucigen essence inserted between the saponite layers is greatly reduced, which affects the luminous effect of composite material, so the concentration of lucigen essence aqueous solution selected by the present invention is 20mg/L L-1000 mg/L, preferably 50 mg/L-800 mg/L, more preferably 100 mg/L-600 mg/L, such as 200 mg/L-400 mg/L.

Step 2, adding the crushed saponite in step 1 into the lucigenin aqueous solution under stirring condition, stirring and standing.

The present inventor finds that the lucigenin of small molecules can be dissolved in water, but the solubility of saponite in water is poor. Therefore, the present invention dissolves lucigenin in water to make a lucigenin aqueous solution. When the lucigenin aqueous solution is mixed with the saponite, the luster The essence can enter the interlayer of the soapstone along with the carrier water, and the intercalation structure of the composite material formed by it and the soapstone is uniform and regular.

The weight of lucigen is based on the weight of solute lucigen in the lucigen solution, the present invention selects the weight ratio of saponite and lucigen to be the weight of saponite: the weight of lucigen=25:1～100:1, preferably 30: 1-90:1, more preferably 45:1-75:1, such as 50:1 or 60:1, etc.

In the present invention, the stirring time is not particularly limited, and it is preferable to fully disperse the saponite in the lucigenin aqueous solution, such as stirring for 1 min to 60 min, preferably 5 min to 50 min, more preferably 10 min to 40 min, such as 15 min.

In step 3, the product obtained in step 2 is heated and stirred, and aged.

The inventors of the present invention have found that under normal temperature conditions, lucigenin is not easy to form a composite material with an intercalation structure with saponite, and the product obtained in step 2 is subjected to heating treatment, especially after the temperature of the system is raised to 50 ° C, in the product The lucigenin can be inserted between the layers of the saponite structure, and the intercalation structure formed is uniform and regular. Therefore, the present invention chooses to heat up the product obtained in step 2. However, the inventor also found that when the processing temperature is higher than At 80°C, the intercalation amount of lucigenin in saponite decreases instead. Therefore, the present invention chooses to heat the product obtained in step 2 to 50°C-80°C, preferably 55°C-70°C, such as 60°C.

In the present invention, the stirring time after heating is not particularly limited, and it is preferred to fully compound the lucigenin and saponite, such as 3h-20h, preferably 4h-15h, more preferably 5h-12h, such as 6h.

Preferably, the product obtained in step 2 is stirred when the temperature of the product obtained in step 2 is raised.

Furthermore, the inventors also found that after aging the product obtained in step 2 after heating treatment, the lucigenite saponite composite material is relatively concentrated in the system, which is convenient for subsequent processing, and the obtained composite material is stable Enhancement, without being bound by any theory, the inventors believe that during the aging process, the lucigenin adsorbed on the surface of the soapstone and the surface of the soapstone reach an adsorption-desorption equilibrium, and the arrangement of the lucigenin between the layers of the saponite It is more uniform and regular, and the amount of intercalation increases, thereby enhancing the stability.

Preferably, the aging is carried out under light-shielding conditions.

In the present invention, the aging time is not particularly limited, and it is preferred to enable the lucigenin and saponite to form a stable composite material, such as 5h-40h, preferably 8h-35h, more preferably 10h-30h, such as 15h-24h.

Step 4, the product obtained in step 3 is separated, washed and dried.

In step 3, the solid phase in the water phase system is the glossy saponite composite material, which is separated from the water phase system, washed and dried to obtain the product.

The present invention does not specifically limit the separation method, and any solid-liquid separation method in the prior art can be used, such as normal pressure filtration, reduced pressure filtration, centrifugal separation and the like.

The present invention chooses to wash the solid obtained after filtration to remove the lucigenin and other soluble impurities that may remain on the surface and are not completely compounded in the soapstone and dissociated.

The inventors found that when the drying temperature is higher than 80°C, the lucigenin in the composite material changes, and its luminescence peak shifts. Therefore, the present invention selects a drying temperature of 50-80°C, preferably 60-70°C. Such as 65°C.

In the prepared lucigenite saponite composite material, the intercalation amount of lucigenin is 0.15mmol/g-0.35mmol/g, preferably 0.16mmol/g-0.28mmol/g; and/or

According to the XRD spectrum, there is an absorption peak at a 2θ angle of about 4.2° to 6°; and/or

According to the fluorescence spectrum, it has an absorption peak at a wavelength of about 550nm.

According to a second aspect of the present invention, there is provided a kind of glossy saponite composite material prepared by the method described in the first aspect above,

The soapstone used is a saponite with a silica-alumina ratio of 3.90/0.10 to 2.50/1.50, preferably 3.74/0.26 to 2.80/1.20; and/or

The intercalation amount of lucigenin is 0.15mmol/g-0.35mmol/g, preferably 0.16mmol/g-0.28mmol/g; and/or

According to the XRD spectrum, there is an absorption peak at a 2θ angle of about 4.2° to 6°; and/or

According to the fluorescence spectrum, it has an absorption peak at about 550 nm.

According to the third aspect of the present invention, the application of the above-mentioned glossy saponite composite material for organic light-emitting molecular devices is provided, which has the advantages of high luminous intensity and strong stability.

The method for preparing glossy saponite composite material provided by the present invention and the glossy saponite composite material prepared by the method have the following beneficial effects:

(1) The preparation method is simple and easy, the preparation conditions are mild, and the operation is simple and convenient;

(2) The raw material is easy to get, cheap, and the production cost is low;

(3) The obtained glossy saponite composite material has stable performance and is not easy to deteriorate;

(4) The thermal stability is enhanced, and it loses its luminous properties at 300°C, while the untreated lucigenin loses its luminous properties at 75°C;

(5) Compared with lucigenin, the composite material has significantly enhanced luminous intensity and significantly prolonged fluorescence lifetime, which can reach 0.2-0.6 μs, which is 26 times higher than that of untreated lucigenin;

(6) Under the same luminous intensity and fluorescence lifetime requirements, the composite material can reduce the amount of gloss essence used, thereby saving the use cost.

Example

Lucigenin (BNMA) used in the following examples, comparative examples and experimental examples of the present invention was purchased from Bailingwei Technology Co., Ltd., and the article number is B1203;

The hydrotalcite used in the comparative example of the present invention was purchased from Jingjiang Kanggaote Plastic Technology Co., Ltd., and the model is fm300.

The measuring method of intercalation amount is ultraviolet spectrophotometry (external standard method), detection wavelength is 230nm.

The measuring method of interlayer spacing is: X-ray powder crystal diffraction, see Experimental Example 1 for details;

For the measurement method of fluorescence lifetime, see Experimental Example 3;

The measurement method of the total energy of the composite material system is to calculate in the CASTEP module through the materials studio6.0 software.

The preparation of embodiment 1 luster essence saponite composite material

(1) Dry the saponite (silicon-aluminum ratio 3.74/0.26, charge per unit cell 0.30, cation exchange capacity 0.92mmol/g) at 50°C for 5h, and crush it to a particle size of 30-50μm; The essence is formulated into a glossy essence aqueous solution with a concentration of 20mg/L;

(2) Add 0.2 g of the crushed saponite in step 1 to 100 mL of luciferin aqueous solution under stirring conditions, stir for 1 min, and let stand for 5 min;

(3) Warm up the product obtained in step 2 to 50°C, stir for 20 hours, and then age in the dark for 5 hours;

(4) Centrifuge the product obtained in step 3 at a centrifugal speed of 3000r/min for 5min, wash the centrifuged solid with distilled water 10 times, and vacuum-dry it at 50°C for 2h.

The amount of intercalation of gloss essence in the prepared gloss essence saponite composite material is 0.28mmol/g, and the interlayer distance is The fluorescence lifetime is 0.201μs, and the total energy of the composite material system is -284.1eV.

The preparation of embodiment 2 luster essence saponite composite material

(1) Dry the saponite (silicon-alumina ratio 3.70/0.30, charge per unit cell 0.37, cation exchange capacity 1.04mmol/g) at 80°C for 1h, and crush it to a particle size of 60-80μm; The essence is formulated into a glossy essence aqueous solution with a concentration of 100mg/L;

(2) Add 0.75 g of the crushed soapstone in step 1 to 100 mL of luciferin aqueous solution under stirring, stir for 60 min, and let stand for 5 min;

(3) Warm up the product obtained in step 2 to 80°C, stir for 3h, and then age in the dark for 40h;

(4) Centrifuge the product obtained in step 3 at a centrifugal speed of 8000 r/min for 1 min, then wash the centrifuged solid with distilled water 6 times, and vacuum-dry it at 80° C. for 1 h.

The intercalation amount of gloss essence in the prepared gloss essence saponite composite material is 0.35mmol/g, and the interlayer distance is The fluorescence lifetime is 0.216μs, and the total energy of the composite material system is -438.6eV.

The preparation of embodiment 3 luster essence saponite composite material

(1) Dry the saponite (silicon-aluminum ratio 3.55/0.45, charge per unit cell 0.41, cation exchange capacity 0.96mmol/g) at 55°C for 4h, and crush it to a particle size of 40-60μm; The essence is formulated into a glossy essence aqueous solution with a concentration of 200mg/L;

(2) Add 1.20 g of the crushed soapstone in step 1 to 100 mL of luciferin aqueous solution under stirring, stir for 50 min, and let stand for 3 min;

(3) Warm up the product obtained in step 2 to 70°C, stir for 4 hours, and then age in the dark for 10 hours;

(4) Centrifuge the product obtained in step 3 at a centrifugal speed of 8000 r/min for 1 min, then wash the centrifuged solid with distilled water for 12 times, and vacuum-dry it at 55° C. for 3 h.

The amount of intercalation of gloss essence in the prepared gloss essence saponite composite material is 0.22mmol/g, and the interlayer distance is The fluorescence lifetime is 0.252μs, and the total energy of the composite material system is -659.6eV.

The preparation of embodiment 4 luster essence saponite composite material

(1) Dry the saponite (silicon-aluminum ratio 3.38/0.62, charge per unit cell 0.44, cation exchange capacity 0.88mmol/g) at 60°C for 4 hours, and crush it to a particle size of 40-70μm; The essence is formulated into a glossy essence aqueous solution with a concentration of 400mg/L;

(2) Add 2.0 g of the crushed soapstone in step 1 to 100 mL of luciferin aqueous solution under stirring conditions, stir for 10 min, and let stand for 5 min;

(3) Warm up the product obtained in step 2 to 55°C, stir for 15 hours, and then age in the dark for 35 hours;

(4) Centrifuge the product obtained in step 3 at a centrifugal speed of 4000r/min for 2min, wash the centrifuged solid with distilled water 4 times, and vacuum-dry it at 60°C for 5h.

The amount of intercalation of gloss essence in the prepared gloss essence saponite composite material is 0.20mmol/g, and the interlayer distance is The fluorescence lifetime is 0.255μs, and the total energy of the composite material system is -684.1eV.

The preparation of embodiment 5 luster essence saponite composite material

(1) Dry the saponite (silicon-alumina ratio 3.27/0.73, charge per unit cell 0.55, cation exchange capacity 0.82mmol/g) at 75°C for 4 hours, and crush it to a particle size of 50-60μm; The essence is formulated into a glossy essence aqueous solution with a concentration of 600mg/L;

(2) Add 1.8 g of the crushed saponite in step 1 to 100 mL of luciferin aqueous solution under stirring conditions, stir for 15 min, and let stand for 8 min;

(3) Warm up the product obtained in step 2 to 60°C, stir for 6h, and then age in the dark for 24h;

(4) Centrifuge the product obtained in step 3 at a centrifugal speed of 5000 r/min for 8 minutes, wash the centrifuged solid with distilled water 8 times, and vacuum-dry it at 70° C. for 4 hours.

The intercalation amount of lucigen essence in the prepared lucigen essence saponite composite material is 0.16mmol/g, and the interlayer distance is The fluorescence lifetime is 0.323μs, and the total energy of the composite material system is -761.8eV.

The preparation of embodiment 6 luster essence saponite composite material

(1) Dry the saponite (silicon-alumina ratio 2.80/1.20, the charge per unit cell is 0.80, and the cation exchange capacity is 0.77mmol/g) at 70°C for 4h, and crush it to a particle size of 70-80μm; The essence is formulated into a glossy essence aqueous solution with a concentration of 600mg/L;

(2) Add 1.8 g of the crushed saponite in step 1 to 100 mL of luciferin aqueous solution under stirring conditions, stir for 40 min, and let stand for 10 min;

(3) Warm up the product obtained in step 2 to 75°C, stir for 12 hours, and then age in the dark for 15 hours;

(4) Centrifuge the product obtained in step 3 at a centrifugal speed of 7000 r/min for 10 minutes, wash the centrifuged solid with distilled water 15 times, and vacuum-dry it at 75° C. for 6 hours.

The intercalation amount of lucigen essence in the prepared lucigen essence saponite composite material is 0.15mmol/g, and the interlayer distance is The fluorescence lifetime is 0.515μs, and the total energy of the composite material system is -889.2eV.

comparative example

Comparative example 1

The method used in this comparative example is the same as that of Example 6, except that the hydrotalcite replaces the soapstone.

The intercalation amount of lucigen essence in the lucigen essence hydrotalcite composite material obtained is 0.08mmol/g, and the interlayer distance is The fluorescence lifetime is 5.03ns, and the total energy of the composite material system is -985eV.

Experimental example

The XRD spectrum measurement of experimental example 1 sample

The instrument used: SHIMADZU/Shimadzu X-ray diffractometer; the model is D/max-2000; the sample is solid powder.

Test conditions: CuKα-irradiation, tube voltage 40 kV, tube current 100 mA, scan speed 2°/min and step size 0.01°.

The samples used in this experimental example are the saponite raw materials used in Examples 1-6 and the samples prepared in Examples 1-6.

The above samples were subjected to XRD testing respectively, and the results are shown in Figure 1a and Figure 1b, wherein Figure 1a shows the XRD spectrum of the saponite raw material used in Examples 1 to 6, and Figure 1b shows the XRD spectra obtained in Examples 1 to 6 The XRD pattern of the sample can be seen from Figure 1a and Figure 1b:

The intercalation amount of lucigenin decreases with the increase of the charge density of the saponite layer, and the intensity of the XRD diffraction peak increases with the increase of the layer charge density.

After lucigenite and the soapstone of different layer charge densities form composite material, the interlayer spacing of soapstone reduces along with the increase of charge density of soapstone raw material layer, by the saponite raw material used in embodiment 1 Reduce to the used saponite raw material of embodiment 6 That is, the greater the layer charge density of the saponite raw material, the smaller the intercalation amount.

Without being bound by any theory, the inventors believe that for a layered structure of saponite, the greater the layer charge density, the stronger the force between the layers, and the less likely the interlayer cations are to be exchanged, resulting in difficulty in the intercalation of luciferin The amount of intercalation decreases, however, after the formation of lucigenite-saponite composites, the force of the saponite sheets on the lucigenins inserted between the layers is enhanced with the increase of the charge density of the sheets.

In addition, the greater the layer charge density of the saponite raw material, the more uniform the intercalation, and the peak shape of the XRD peak is symmetrical and sharp, indicating that the stacking degree and order of the lucigenin between the saponite layers increase, and the lucigenin-saponite composite enhanced stability.

The fluorescence emission spectrum of experimental example 2 samples

Instrument used: Hitachi brand F4600 fluorescence spectrophotometer.

Test conditions: The photomultiplier tube is operated at 400V, and a 150w xenon lamp is used as the excitation source.

The samples used in this experimental example are the samples prepared in Examples 1-6 and untreated lucigenin products.

The above samples were tested by fluorescence emission spectrum, and the results are shown in Figure 2, as can be seen from Figure 2:

The composite functional material presents a symmetrical and sharp peak at 550nm, indicating that the lucigenin is arranged in a single layer between the saponite layers, and the fluorescence intensity of the composite material at this location gradually increases with the increase of the layer charge density.

The fluorescence emission spectrum of the composite functional material has no red shift and broadening phenomenon, indicating that there is no obvious molecular aggregation in the whole intercalation process.

However, the intensity of the emission spectrum of BNMA is very weak, the peak shape is broadened, and the luminescence performance is poor.

The XRD diffraction pattern further indicated that the composite functional material exhibited a highly periodic ordered layered structure, corresponding to a single cycle of lucigenin/saponite assembly units.

Fluorescence lifetime measurement of experimental example 3 sample

Test conditions: The British LifeSpec-ps time-correlated single-electron counting lifetime spectrometer is used to measure the fluorescence time-resolved delay curve under 375nm laser excitation; F900 software is used to fit the fluorescence lifetime of the system.

The samples used in this experimental example are the samples prepared in Examples 1-6 and the lucigenin aqueous solution with a concentration of 100 mg/L.

Due to the severe concentration quenching of lucigenin solids, that is, the extremely short fluorescence lifetime, existing instruments cannot capture its fluorescence lifetime. Therefore, in this experimental example, lucigenin was diluted with an aqueous solution to obtain the fluorescence lifetime of lucigenin.

The above-mentioned samples were subjected to fluorescence lifetime measurement, and the results are shown in Figure 3, wherein,

Curve A represents the fluorescence time-resolved delay curve of the sample obtained in Example 1, curve B represents the fluorescence time-resolved delay curve of the sample obtained in Example 2, curve C represents the fluorescence time-resolved delay curve of the sample obtained in Example 3, and curve D It represents the fluorescence time-resolved delay curve of the sample obtained in Example 4, the curve E represents the fluorescence time-resolved delay curve of the sample obtained in Example 5, and the curve F represents the fluorescence time-resolved delay curve of the sample obtained in Example 6.

It can be seen from Figure 3 that:

The fluorescence lifetime of the lucigenin aqueous solution is only 0.02μs, and after the lucigenin is inserted into the soapstone layer to form the lucigenin-saponite composite material, the composite material can not only emit light in a solid state, but also its fluorescence lifetime can be extended to 0.515μs at most, corresponding to 26 times higher than gloss essence.

Experimental example 4 sample heat resistance performance test

Luminescent materials have to experience the test of constantly changing ambient temperature during use. During this process, the luminescent properties of materials will change significantly. Therefore, the thermal stability of luminescent materials is an important reference to determine its application field.

Instrument used: Hitachi brand F4600 fluorescence spectrophotometer.

Experimental method: After heating the sample to different temperatures, measure its fluorescence spectrum.

The samples used in this experimental example are the sample prepared in Example 6 and the untreated lucigenin product.

The above-mentioned samples were tested for heat resistance, the heat resistance result of luciferin is shown in Figure 4a, and the heat resistance result of the sample prepared in Example 6 is shown in Figure 4b, as can be seen from Figure 4a and Figure 4b:

The luminous intensity of BNMA weakens with the increase of temperature, and has basically lost its luminous properties at 75 °C.

Although the luminous intensity of the glossy saponite composite material also decreases with the increase of temperature, it does not lose its luminous performance until 300℃.

That is, the lucigenite composite material also has improved thermal stability relative to lucigen.

Without being bound by any theory, the inventors believe that BNMA is in the interlayer domain of saponite, and the electrostatic force exerted by saponite sheets on it protects it, making it more adaptable to environmental temperature changes.

Calculation of forbidden band width of experimental example 5 samples

Calculate with materials studio6.0 software.

The samples used in this experimental example are the sample prepared in Example 6 and the untreated lucigenin product.

Determination of the calculated energy band structure of the above samples, wherein the energy band diagram of the untreated lucigenin product is shown in Figure 5a1, and its density of state diagram is shown in Figure 5a2;

The energy band diagram of the sample obtained in Example 6 is shown in Figure 5b1, and its density of state diagram is shown in Figure 5b2;

From Figure 5a1, Figure 5a2, Figure 5b1, and Figure 5b2, we can see that:

Saponite raw materials with different layers of charge have different interactions with the interlayer gloss essence. When the lucigenin is independently distributed in vacuum, the energy gap is about 1.03ev, which is lower than the top of the valence band, and the concentration quenching effect occurs, and the luminous intensity is very low; when the lucigenin is inserted into the saponite layer, the energy gap is 3.72ev. Between the valence band and the conduction band, energy level transitions are easy to occur and emit light.

The width between the valence and conduction bands determines the wavelength at which the atomic orbitals of BNMA transition. Calculated according to the energy level transition formula E=hv=hc/λ, the wavelength of the emission spectrum is 537nm, which is basically consistent with the wavelength data in the actual emission spectrum, and is in the wavelength range of green light.

The solid nuclear magnetic test of the used saponite raw material of experimental example 6

Instrument used: Bruker company AVANCEIII400WB nuclear magnetic analyzer.

The sample used in this experimental example is the saponite raw material used in Examples 1 to 6. The above-mentioned raw materials are respectively subjected to ²⁷ Al magic angle rotation method nuclear magnetic resonance spectroscopy test and ²⁹ Si cross polarization magic angle rotation method nuclear magnetic resonance spectroscopy test. The results are respectively as follows Figure 6a and Figure 6b.

From the NMR spectrum of ²⁷ Al magic angle rotation method (Figure 6a), it can be seen that:

Al(IV) has a resonance wavelength around 65 ppm, which is stronger than Al(VI) resonating at 9 ppm, indicating that Al tends to occupy tetrahedral sites rather than octahedral sites.

In addition, as the Si/Al ratio decreases, that is, the Al content in saponite increases, the peak intensity at 9 ppm gradually increases, indicating that the Al(VI) at the octahedron gradually increases, further indicating that Al preferentially enters the tetrahedron.

From the ²⁹ Si cross-polarized magic-angle rotation NMR spectrum (Fig. 6b), it can be seen that:

The signals of ²⁹ Si appear at about -95ppm, -91ppm and -86ppm, corresponding to Q ³ Si(0Al), Q ³ Si(1Al) and Q ³ Si(2Al), respectively.

As the Si/Al ratio in the saponite raw material decreases, the signal intensity of Q ³ Si(0Al) decreases gradually, and the signal intensity of Q ³ Si(1Al) gradually increases, indicating that the aluminum content in the tetrahedral sheets increases, and in all samples On the ²⁹ Si cross-polarization magic angle rotation method nuclear magnetic resonance spectrum, there is a signal of Q ³ Si (2Al) at about -84ppm to -86ppm.

The signal at -86ppm is caused by the appearance of ^Q2Si (OAl) at the edge of the saponite layer, without being bound by any theory, the inventors believe that ^Q3Si (2Al) and ^Q2Si (OAl) at -86ppm ) common signal.

As the Si/Al ratio in the saponite raw material decreases, the peak area at -86ppm increases gradually, indicating that the signals of Q ³ Si(2Al) and Q ² Si(OAl) increase; while the Si/Al ratio is At 3.38/0.62, the signal at -86ppm decreases suddenly, and then increases with the decrease of Si/Al ratio.

By comparing Q ³ Si(0Al), the signal intensity of Q ³ Si(1Al) changes with Si/Al, without being bound by any theory, the inventor believes that when Si/Al is larger, the signal intensity at -86ppm The signal is dominated by Si(OAl), and with the decrease of Si/Al, the signal at -86ppm is gradually dominated by the signal of Q ³ Si(2Al), which is consistent with the conclusion that the content of Al in saponite increases gradually .

In addition, because the electronegativity of Al is smaller than that of Si, the chemical shifts of Q ³ Si(1Al) and Q ³ Si(2Al) peaks will move downfield after isomorphism.

Therefore, spectral peaks appeared at -92.5ppm, -89ppm, and -85ppm respectively in the soapstone raw materials used in Example 5 and Example 6, without being bound by any theory. The spectral peaks of Q ³ Si(0Al), Q ³ Si(1Al) and Q ³ Si(2Al) all shifted downfield.

Based on the above experiments, without being bound by any theory, the inventors believe that the content of Al in the tetrahedron will determine the layer charge of saponite. The more Al content, the more layer charge will be, and the stronger the electric field intensity between layers will be. With the decrease of Si/Al, the charge of saponite layer increases gradually.

The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that without departing from the spirit and scope of the present invention, various equivalent replacements, modifications or improvements can be made to the technical solutions and implementations of the present invention, all of which fall within the scope of the present invention. The protection scope of the present invention shall be determined by the appended claims.

Claims (12)

1. the method preparing lucigenin smectite composite material, it is characterised in that the method comprises the following steps:

(1) saponite being dried when temperature is 50 DEG C～80 DEG C 1～5 hour, pulverizes, the particle diameter of saponite granule is 30 μm～80 μm, and lucigenin is formulated as lucigenin aqueous solution, and the concentration of lucigenin aqueous solution is 20mg/L～1000mg/L；

(2) saponite after pulverizing in step 1 is joined in lucigenin aqueous solution under agitation, stirring, standing, the weight of lucigenin is with the weight that weight ratio is saponite of the weighing scale of solute lucigenin in lucigenin aqueous solution, saponite and lucigenin: the weight=25:1～100:1 of lucigenin；

(3) product obtained in step 2 is warming up to 50 DEG C～80 DEG C stirrings, ageing 5h～40h；

(4) product obtained in step 3 is separated, washing and temperature be under 50 DEG C～80 DEG C conditions dry,

In prepared lucigenin smectite composite material, the intercalation amount of lucigenin is 0.15mmol/g～0.35mmol/g.

2. method according to claim 1, it is characterised in that in step 1, saponite used is silica alumina ratio is the saponite of 3.90/0.10～2.50/1.50.

3. method according to claim 2, it is characterised in that in step 1, saponite used is silica alumina ratio is the saponite of 3.74/0.26～2.80/1.20.

4. method according to claim 1, it is characterised in that in step 1,

It is dried when temperature is 55 DEG C～70 DEG C；And/or

Dry 2～4 hours；And/or

The particle diameter of saponite granule is 40 μm～70 μm；And/or

The concentration of lucigenin aqueous solution is 50mg/L～800mg/L.

5. the method according to any one of Claims 1 to 4, it is characterized in that, in step 2, the weight of lucigenin is with the weight that weight ratio is saponite of the weighing scale of solute lucigenin in lucigenin aqueous solution, saponite and lucigenin: the weight of lucigenin is 30:1～90:1.

6. method according to claim 5, it is characterised in that in step 2, the weight of lucigenin is with the weight that weight ratio is saponite of the weighing scale of solute lucigenin in lucigenin aqueous solution, saponite and lucigenin: the weight of lucigenin is 45:1～75:1.

7. the method according to any one of Claims 1 to 4, it is characterised in that in step 2, adds saponite to lucigenin aqueous solution, stirs 1min～60min.

8. method according to claim 7, it is characterised in that in step 2, adds saponite to lucigenin aqueous solution, stirs 5min～50min.

9. method according to claim 8, it is characterised in that in step 2, adds saponite to lucigenin aqueous solution, stirs 10min～40min.

10. the method according to any one of Claims 1 to 4, it is characterised in that in step 3,

The product obtained in step 2 is warming up to 55 DEG C～70 DEG C；And/or

Ageing 8h～35h.

11. the method according to any one of Claims 1 to 4, it is characterised in that in step 4, it is dry under 60 DEG C～70 DEG C conditions in temperature.

12. the method according to any one of Claims 1 to 4, it is characterised in that

In prepared lucigenin smectite composite material, the intercalation amount of lucigenin is 0.16mmol/g～0.28mmol/g；And/or

Composing according to XRD, it is that 4.2 °～6 ° places exist absworption peak at 2 θ angles；And/or

According to fluorescence spectrum, there is absworption peak at wavelength 550nm place in it.