Europium-based light conversion agent for agricultural film as well as preparation method and application of europium-based light conversion agent

Abstract

The invention discloses a europium-based light conversion agent for an agricultural film and a preparation method and application of the europium-based light conversion agent, the chemical formula of the light conversion material is Eu2 (C7H5IO2) 6 (C12H8N2) 2, and the molecular formula of the material is C66H46O12N4I6Eu2. The preparation method comprises the following steps: dissolving 3-iodobenzoic acid and phenanthroline in ethanol, then adding an aqueous solution of EuCl3. 6H2O, and carrying out solvothermal reaction and cooling to obtain colorless flaky crystals, namely the red light conversion material Eu2 (C7H5IO2) 6 (C12H8N2) 2. The light conversion material disclosed by the invention generates red fluorescence with the intensity of 7.7 * 10 < 7 > a.u. Under the irradiation of incident light with the wavelength of 334 nm; and red fluorescence with the intensity of 2.7 * 10 < 6 > a.u. Is generated under the irradiation of incident light with the wavelength of 544 nm. The preparation process is simple, chemical components are easy to control, repeatability is good, and solubility is good.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of light conversion agent material preparation, in particular to a europium-based light conversion agent for agricultural film and a preparation method and application thereof. BACKGROUND

[0002] Photoecology research shows that red-orange light with a wavelength of 600-680 nm is most effective for plant growth, green-yellow light with a wavelength of 510-580 nm is largely reflected by the stems and leaves of crops, and ultraviolet light with a wavelength of 290-400 nm has an adverse effect on the growth of crops, not only causing poor crop development, but also inducing certain pests and diseases, and having a strong photo-oxidative damage effect on polymers such as plastic agricultural films. Therefore, a light conversion agent that can actively convert ultraviolet light and green-yellow light that is not useful for crop growth into red-orange light has great significance. Adding the light conversion agent to agricultural films to produce light conversion agricultural films can not only improve the utilization rate of sunlight by crops, increase crop yield, and improve the quality of agricultural products, but also prolong the service life of the agricultural films. Although there are many related studies on rare earth red light conversion agents in China, there are still few studies on light conversion agents that can convert ultraviolet light and green light into red light and have good solubility. SUMMARY

[0003] To improve the above technical problems, the present application provides a europium-based light conversion agent for agricultural film and a preparation method and application thereof, wherein the Eu2(C7H5IO2)6(C 12 H8N2)2 light conversion material can convert ultraviolet light and green light into red fluorescence.

[0004] To achieve the above-mentioned application purposes, the present application adopts the following technical solutions:

[0005] The present application provides a red light conversion material, which has a chemical formula of Eu2(C7H5IO2)6(C 12 H8N2)2.

[0006] According to an embodiment of the present application, the red light conversion material belongs to the triclinic system, and the space group is P-1, and the cell parameters are approximately α=95.061°, β=100.686°, γ=97.477°.

[0007] According to an embodiment of the present application, the cell volume of the crystal material is 1635.37(11).

[0008] According to an embodiment of the present application, the number of molecules in the cell of the crystal material is Z=13.

[0009] According to an embodiment of the present application, the light conversion material has a crystal structure as shown in Figure 1 .

[0010] According to the embodiment of the present application, the molecular formula of the light conversion material is: C 66 H 46 O 12 N4I6Eu2, and the molecular weight is 2152.45.

[0011] According to the embodiment of the present application, the light conversion material is a colorless sheet crystal.

[0012] According to the embodiment of the present application, the crystal structure data of the light conversion material is shown in Table 1, and the relevant bond length and bond angle are shown in Table 2.

[0013] Table 1: Crystallographic parameters of Eu2(C7H5IO2)6(C 12 H8N2)2

[0014]

[0015] Table 2: Bond length and bond angle of Eu2(C7H5IO2)6(C 12 H8N2)2 and bond angle (°)

[0016]

[0017]

[0018] Symmetry code: (i) -x, -y, -z.

[0019] According to the embodiment of the present application, the light conversion material Eu2(C7H5IO2)6(C 12 H8N2)2 generates red fluorescence of 7.7 x 10 7 a.u. intensity under the irradiation of incident light at 334 nm, and generates red fluorescence of 2.7 x 10 6 a.u. intensity under the irradiation of incident light at 544 nm.

[0020] According to the embodiment of the present application, the light conversion material is a red light conversion material, which can convert ultraviolet light and green light into red fluorescence.

[0021] The present application also provides a preparation method of the above-mentioned red light conversion material, which comprises preparing the red light conversion material Eu2(C7H5IO2)6(C 12 H8N2)2 by solvothermal synthesis method using 3-iodobenzoic acid, phenanthroline and EuCl3·6H2O.

[0022] According to the embodiment of the present application, the reaction weight ratio of the 3-iodobenzoic acid, phenanthroline and EuCl3·6H2O is (0.037-0.074):(0.014-0.028):(0.027-0.054).

[0023] According to an embodiment of the present invention, the 3-iodobenzoic acid, o-phenanthroline, and EuCl3·6H2O are all mixed in solution form before the reaction. For example, ethanol solutions of 3-iodobenzoic acid and o-phenanthroline and an aqueous solution of EuCl3·6H2O are prepared separately, and then the two solutions are mixed to obtain a mixed solution.

[0024] According to an embodiment of the present invention, the concentration of 3-iodobenzoic acid in the ethanol solution is 0.01 to 0.015 g / ml, for example 0.0123 g / ml.

[0025] According to an embodiment of the present invention, the concentration of o-phenanthroline in the ethanol solution is 0.004 to 0.005 g / ml, for example 0.0047 g / ml.

[0026] According to an embodiment of the present invention, the concentration of EuCl3·6H2O in the aqueous solution is 0.01 to 0.02 g / ml, and exemplarily 0.018 g / ml.

[0027] According to an embodiment of the present invention, after the two solutions are mixed, the mixed solution can be subjected to ultrasound. For example, the ultrasound time is 5 to 20 minutes, exemplarily 10 minutes.

[0028] According to an embodiment of the present invention, the temperature of the solvothermal synthesis method is 90-100°C, exemplarily 95°C; the time of the solvothermal synthesis method is 10-20 hours, exemplarily 15 hours.

[0029] According to an embodiment of the present invention, the preparation method of the red light-converting material includes the following steps:

[0030] 3-Iodobenzoic acid and o-phenanthroline are dissolved in ethanol to obtain an ethanol solution, and EuCl3·6H2O is dissolved in water to obtain an aqueous solution. The two solutions are then mixed, ultrasonically vibrated, and then heated at 90-100℃ for 10-20 hours. After cooling, colorless flaky crystals are obtained, which are the red light-converting materials.

[0031] The present invention also provides the application of the above-mentioned europium-based optical conversion material in agricultural films.

[0032] The present invention also provides an agricultural film containing the above-mentioned europium-based optical conversion material and / or prepared from the above-mentioned europium-based optical conversion material.

[0033] The present invention also provides a method for improving the utilization rate of sunlight by crops, increasing crop yield, and improving the quality of agricultural products, including using the above-mentioned agricultural film during the crop growth process.

[0034] Beneficial effects of the present invention: The red light-converting material Eu2(C7H5IO2)6(C) of the present invention 12 The raw materials for preparing H8N2)2 are readily available, have excellent fluorescence properties, and exhibit light conversion effects. It can be prepared by solvothermal synthesis, which is simple, easy to control chemical composition, has good repeatability, and good solubility. Attached Figure Description

[0035] Figure 1 The red light-converting material Eu2(C7H5IO2)6(C) provided in the embodiments of the present invention 12 Crystal structure diagram of H8N2)2;

[0036] Figure 2 In Figures (a) and (b), Eu2(C7H5IO2)6(C) provided in Embodiment 2 of the present invention are respectively 12 Fluorescence spectra of H8N2)2 under incident light at 334 nm and 544 nm.

[0037] Figure 3 The prepared agricultural film is used for plant growth. Detailed Implementation

[0038] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0039] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0040] This invention provides a red-emitting light-converting material, the name of which is: Eu2(C7H5IO2)6(C 12 H8N2)2, molecular formula C 66 H 46 O 12 N4I6Eu2, with a molecular weight of 2152.45. Crystal structure data are shown in Table 1, and key bond lengths and angles are shown in Table 2; this red fluorescent material Eu2(C7H5IO2)6(C 12 H8N2)2 produces 7.7 × 10⁻⁶ ppm under incident light at 334 nm. 7 The red fluorescence of au intensity produces 2.7 × 10⁻⁶ under incident light at 544 nm. 6 au intensity red fluorescence;

[0041] Table 1: Eu2(C7H5IO2)6(C 12 Crystallographic parameters of H8N2)2

[0042]

[0043] Table 2: Eu2(C7H5IO2)6(C 12 H8N2)2 bond length Bond angle (°)

[0044]

[0045]

[0046] Symmetric codes: (i)-x,-y,-z.

[0047] The aforementioned red light-converting material Eu2(C7H5IO2)6(C 12 H8N2)2 was synthesized using a solvothermal method. The specific synthesis steps are as follows:

[0048] Dissolve 0.037–0.074 g of 3-iodobenzoic acid and 0.014–0.028 g of o-phenanthroline in 3–6 ml of ethanol solution. Then dissolve 0.027–0.054 g of europium chloride hexahydrate in 1.5–3 ml of distilled water. Place the solutions in a small vial, sonicate for 10 minutes, and then heat in a 95°C oven for 15 hours. After cooling, colorless flaky crystals, namely Eu2(C7H5IO2)6(C 12 H8N2)2; its structure was determined using a single-crystal diffractometer. Fluorescence testing was performed on the material, and it produced a fluorescence of 7.7 × 10⁻⁶ under incident light at 334 nm. 7 The red fluorescence of au intensity produces 2.7 × 10⁻⁶ under incident light at 544 nm. 6 A red fluorescence of au intensity.

[0049] Example 1

[0050] 0.037 g of 3-iodobenzoic acid and 0.014 g of o-phenanthroline were dissolved in 3 ml of ethanol to obtain an ethanol solution. 0.027 g of EuCl3·6H2O was dissolved in 1.5 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small vial. The solution was ultrasonically vibrated for 10 minutes, then heated in a 95°C oven for 15 hours. After cooling, colorless flaky crystals were obtained, which is the red-converting material Eu2(C7H5IO2)6(C 12 H8N2)2.

[0051] The product was characterized using the following instruments and methods: 1. Select samples with dimensions of 0.25 × 0.25 × 0.26 mm. 3The crystal was used for single-crystal structure analysis. Single-crystal diffraction data were collected on a Bruker-AXS SMART APEX2 CCD diffractometer, monochromated with Mok α rays using a graphite monochromator. 1.6°≤θ≤26.4°, the crystal structure of the light-converting material obtained in this embodiment is shown in [reference needed]. Figure 1 (Drawn using Diamond software). The results in the figure show that the optical conversion material Eu2(C7H5IO2)6(C) of the present invention... 12 H8N2)2 belongs to the triclinic crystal system, with space group P-1 and a unit cell parameter of approximately 1. α=95.061°, β=100.686°, γ=97.477°.

[0052] Example 2

[0053] 0.074 g of 3-iodobenzoic acid and 0.028 g of o-phenanthroline were dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of EuCl3·6H2O was dissolved in 3 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small vial. The solution was ultrasonically vibrated for 10 minutes, then heated in a 95°C oven for 15 hours. After cooling, colorless flaky crystals were obtained, which is the red-converting material Eu2(C7H5IO2)6(C 12 H8N2)2.

[0054] The red light-converting material Eu2(C7H5IO2)6(C) prepared in this embodiment 12 Fluorescence testing was performed on H8N2)2, and the resulting fluorescence spectrum curves are shown below. Figure 2 As shown in (a) and (b) in the figure. The results in the figure show that the Eu2(C7H5IO2)6(C) of the present invention... 12 H8N2)2 produces 7.7 × 10⁻⁶ ppm under incident light at 334 nm. 7 The red fluorescence of au intensity produces 2.7 × 10⁻⁶ under incident light at 544 nm. 6 A red fluorescence of au intensity.

[0055] Comparative Example 1

[0056] 0.074 g of 3-iodobenzoic acid and 0.028 g of o-phenanthroline were dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of EuCl3·6H2O was dissolved in 3 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small bottle. The mixture was ultrasonically vibrated for 10 minutes and then heated in an oven at 75°C for 15 hours. After cooling, the crystalline red light-converting material was obtained.

[0057] Comparative Example 2

[0058] 0.074 g of 3-iodobenzoic acid and 0.028 g of o-phenanthroline were dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of EuCl3·6H2O was dissolved in 3 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small bottle. The mixture was ultrasonically vibrated for 10 minutes and then heated in an oven at 120°C for 15 hours. After cooling, the crystalline red light-converting material was obtained.

[0059] Comparative Example 3

[0060] 0.074 g of 3-iodobenzoic acid and 0.028 g of o-phenanthroline were dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of Eu(NO3)3·6H2O was dissolved in 3 ml of distilled water to obtain an Eu(NO3)3·6H2O solution. The Eu(NO3)3·6H2O solution was then added to the above ethanol solution and placed in a small bottle. The mixture was ultrasonically vibrated for 10 minutes and then heated in an oven at 95°C for 15 hours. After cooling, the crystalline red light-converting material was obtained.

[0061] Comparative Example 4

[0062] 0.074 g of 3-iodobenzoic acid was dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of EuCl3·6H2O was dissolved in 3 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small bottle. The mixture was ultrasonically vibrated for 10 minutes and then heated in an oven at 95°C for 15 hours. After cooling, the crystalline red light-converting material was obtained.

[0063] Comparative Example 5

[0064] 0.074 g of 3-iodobenzoic acid was dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of EuCl3·6H2O was dissolved in 3 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small bottle. The mixture was ultrasonically vibrated for 10 minutes and then heated in an oven at 95°C for 15 hours. After cooling, the crystalline red light-converting material was obtained.

[0065] Comparative Example 6

[0066] 0.028 g of o-phenanthroline was dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of EuCl3·6H2O was dissolved in 3 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small bottle. The mixture was ultrasonically vibrated for 10 minutes and then heated in an oven at 95°C for 15 hours. After cooling, the crystalline red light-converting material was obtained.

[0067] Comparative Example 7

[0068] 0.074 g of 3-iodobenzoic acid and 0.028 g of o-phenanthroline were dissolved in 6 ml of ethanol to obtain an ethanol solution. 0.054 g of EuCl3·6H2O was dissolved in 3 ml of distilled water to obtain an EuCl3·6H2O solution. The EuCl3·6H2O solution was then added to the above ethanol solution and placed in a small bottle. The mixture was ultrasonically vibrated for 10 minutes and then heated in an oven at 95°C for 5 hours. After cooling, the crystalline red light-converting material was obtained.

[0069] Test case

[0070] The light-converting material prepared in Example 2 above was mixed with a polyurethane polymer solution to prepare an agricultural film with a mass fraction of 1% light-converting material.

[0071] The agricultural film prepared in this embodiment was used in the plant cultivation process, and the results were as follows: Figure 3 As shown in the figure, it can be seen that the plants grown using the agricultural film prepared with the light-converting material of the present invention (right side) exhibit significantly stronger growth than the plants grown using the agricultural film without the light-converting material of the present invention (left side).

[0072] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A light conversion material, characterized in that The chemical formula of the light conversion material is: Eu2(C7H5IO2)6(C 12 H8N2)2.

2. The light conversion material of claim 1, wherein, The light conversion material belongs to triclinic system, space group is P-1, and the cell parameters are about α = 95.061°, β = 100.686°, γ = 97.477°.

3. The method of producing a light conversion material according to claim 1 or 2, characterized in that, The preparation method comprises preparing the light conversion material Eu2(C7H5IO2)6(C 12 H8N2)2 by a solvothermal synthesis method through 3-iodobenzoic acid, o-phenanthroline and EuCl3·6H2O.

4. The production method according to claim 3, wherein The reaction weight ratio of the 3-iodobenzoic acid, o-phenanthroline and EuCl3·6H2O is (0.037-0.074):(0.014-0.028):(0.027-0.054).

5. The production method according to claim 3, wherein The temperature of the solvothermal synthesis method is 90-100℃; the time of the solvothermal synthesis method is 10-20h.

6. The production method according to any one of claims 3 to 5, wherein The method comprises the following steps: dissolving 3-iodobenzoic acid and o-phenanthroline in ethanol to obtain an ethanol solution, dissolving EuCl3·6H2O in water to obtain an aqueous solution, mixing the two solutions, ultrasonic oscillation, and then heating reaction at 90-100℃ for 10-20h, and cooling to obtain colorless flaky crystals, which are the light conversion material.

7. Application of the light conversion material of claim 1 or 2 and / or the light conversion material prepared by the preparation method of any one of claims 3-6 in agricultural films.

8. An agricultural film characterized by, It contains the light conversion material of claim 1 or 2 and / or the light conversion material prepared by the preparation method of any one of claims 3-6 and / or is prepared from the light conversion material of claim 1 or 2 and / or the light conversion material prepared by the preparation method of any one of claims 3-6.

9. A method for improving the utilization of sunlight by a crop, increasing the yield of a crop, improving the quality of an agricultural product, characterized by, It comprises using the agricultural film of claim 8 during crop growth.

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