Organic-inorganic hybrid full-color light absorbing material and preparation method thereof

Abstract

The invention discloses a novel organic-inorganic hybrid light absorption material which is formed by combining N, N '-bis (N, N-dimethylethylamino)-1, 4, 5, 8-naphthalimide serving as an organic element and silicomolybdic acid [SiMo12O40] 4-anion serving as an inorganic element through electrostatic acting force and supramolecular acting force. The preparation method is characterized in that the product has very strong light absorption capacity from an ultraviolet region to a near-infrared region, the absorption edge can reach 2500 nm or above, and the product has good chemical stability and light stability and has a certain application prospect in the fields of photocatalysis, solar cells, photoelectric detectors, photo-thermal conversion and the like.

Description

Technical Field

[0001] The present invention belongs to the field of photosensitive materials, and particularly relates to a novel organic-inorganic hybrid light-absorbing material and a preparation method thereof. Background Art

[0002] As a core component of optoelectronic conversion devices, light-absorbing materials have important applications in fields such as solar cells, photodetectors, and photocatalysis. Although traditional organic light-absorbing materials have advantages such as strong molecular structure tunability and low preparation cost, their light absorption range mostly focuses on the ultraviolet and visible light regions (200 - 700 nm), and their absorption ability for near-infrared light (>700 nm), which accounts for nearly 50% of the solar energy, is weak, and there are also defects in poor photothermal stability. Inorganic materials (such as metal oxides, perovskites, quantum dots, etc.) show excellent performance in wide-spectrum absorption, but their bandgap regulation flexibility is poor, and some materials contain toxic metal elements (such as Pb), which limits their practical applications.

[0003] In recent years, organic-inorganic hybrid materials have combined the advantages of both through molecular design and become a research hotspot. For example, the organic lead halide perovskite materials reported in the literature show broadband response characteristics, but the toxicity of lead and poor environmental stability limit their applications; Patent CN110627709A proposes a bismuth halide-based hybrid perovskite containing 4-phenylpyridine with a hydrophobic alkyl group, which solves the problems of poor material stability and high toxicity, but has poor response ability to near-infrared light; Patent CN200710135874 proposes a light absorber based on a substituted benzene dithiol metal coordination compound, which has good absorption ability for near-infrared light in the range of 800 - 1100 nm, but the light energy utilization rate in the near-infrared region above 1100 nm is insufficient. In addition, existing hybrid materials generally have problems such as discontinuous absorption spectra and low absorption efficiency in specific bands, especially insufficient light energy utilization rate in the near-infrared region (800 - 2500 nm), which restricts the further improvement of device performance.

[0004] Based on the above technical problems, there is an urgent need to develop an organic-inorganic hybrid material with strong absorption in a broadband (ultraviolet-visible-near-infrared), high stability, and simple preparation process. The objective of the present invention is to construct an organic-inorganic donor-acceptor hybrid material through innovative structural design to achieve efficient light capture in the entire wavelength range, while having good environmental stability and photostability, and providing a new material solution for high-performance optoelectronic devices. Summary of the Invention

[0005] The objective of the present invention is to provide a novel organic-inorganic hybrid light-absorbing material and a preparation method thereof.

[0006] To achieve the above objective, the present invention adopts the following technical solutions:

[0007] An organic-inorganic hybrid light absorption material, which uses N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide (named: NDIDMA) as the organic moiety and silicomolybdic acid [SiMo 12 O 40 4- anion as the inorganic moiety, and is formed by combining through electrostatic force and supramolecular force.

[0008] Specifically, its molecular formula is C 44 H 52 Mo 12 N8O 48 Si, with a molecular weight of 2640.29, it is a monoclinic single crystal, the space group is P21 / c, and the unit cell parameters are: α = 90°, β = 95.849(7)°, γ = 90°, Z = 4.

[0009] The preparation of the organic-inorganic hybrid light absorption material is to slowly drip a mixed solution of dimethylformamide / methanol onto a dimethylformamide solution containing hydroiodic acid and N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide to form a layer; then continue to slowly drip a methanol solution containing silicomolybdic acid onto a mixed solution of dimethylformamide / acetonitrile to form a layer. After standing in the dark, the organic-inorganic hybrid light absorption material is obtained.

[0010] Further, in the mixed solution of dimethylformamide / methanol, the volume ratio of dimethylformamide to methanol is 1:1.

[0011] Further, the hydroiodic acid is an aqueous solution with a concentration of 55%.

[0012] Further, in the dimethylformamide solution containing hydroiodic acid and N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide, the content of N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide is 0.012 mmol / mL, and the content of hydroiodic acid is 0.02 mL / mL.

[0013] Further, in the methanol solution containing silicomolybdic acid, the content of silicomolybdic acid is 0.006 mmol / mL.

[0014] Further, the volume ratio of the methanol solution containing silicomolybdic acid, the mixed solution of dimethylformamide / methanol, and the dimethylformamide solution containing hydroiodic acid and N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide is 5:1:5.

[0015] ​Furthermore, the standing time in the dark is 5 days.

[0016] The significant advantages of the present invention are as follows:

[0017] The organic-inorganic hybrid light absorption material prepared by the present invention is black, has strong light absorption ability in the ultraviolet to near-infrared regions, the absorption edge can reach more than 2500 nm, and the product shows good stability under both environmental conditions and light conditions, and has certain application prospects in the fields of photocatalysis, solar cells, photodetectors, photothermal conversion, etc. Description of the Drawings

[0018] Figure 1 It is the crystal structure diagram of the light absorption material prepared for the example.

[0019] Figure 2 It is the sample photo of the light absorption material prepared for the example.

[0020] Figure 3 It is the absorption spectrum diagram of the light absorption material prepared for the example before and after illumination.

[0021] Figure 4 It is the powder diffraction pattern of the light absorption material prepared for the example before and after illumination.

[0022] Figure 5 It is the infrared absorption spectrum diagram of the light absorption material prepared for the example before and after illumination.

[0023] Figure 6 It is the 1 H-nuclear magnetic resonance spectrum of N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide in deuterated chloroform. Detailed Embodiments

[0024] In order to make the content described in the present invention easier to understand, the technical solutions of the present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited thereto.

[0025] The preparation process of N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide (NDIDMA) is as follows: Suspend 1,4,5,8-naphthalenetetracarboxylic dianhydride (2 g, 7.46 mmol) in 80 mL of water, heat and stir until dissolved. Subsequently, add N,N-dimethylethylenediamine (2.35 g, 26.7 mmol) to the above solution, and stir and react at 80 °C for 12 hours. After cooling to room temperature, collect the generated precipitate by suction filtration, and wash it with 30 mL of acetone and 30 mL of water. Dry the wet precipitate under high vacuum to obtain a yellow-orange solid (2.82 g, 6.90 mmol, yield 93%).

[0026] Example 1

[0027] The light absorption material is synthesized by a diffusion method, using NDIDMA as the organic building block and H3PW 12 O 40 as the inorganic building block. Specifically, 1 mL of a mixed solution of dimethylformamide / methanol (1:1, v / v) is slowly added dropwise onto 5 mL of a dimethylformamide solution containing 55% hydroiodic acid aqueous solution (0.1 ml) and N,N'-bis(N,N-dimethylamino)-1,4,5,8-naphthalenediimide (0.06 mmol, 24.5 mg), forming a layered structure; then 5 mL of a methanol solution containing silicomolybdic acid (0.03 mmol, 54.7 mg) is slowly added dropwise onto the dimethylformamide / acetonitrile mixed solution, also forming a layered structure. After standing in the dark for 5 days, black crystals are obtained, with a yield of approximately 57% (calculated based on the amount of silicomolybdic acid).

[0028] The obtained product is characterized and its performance is tested as follows:

[0029] (1) Crystal structure determination

[0030] Single crystals with appropriate size and regular shape are selected under a microscope. Using a Bruker APEX II CCD diffractometer, at 293(2) K, Mo-K α rays monochromatized by a graphite monochromator are used as the incident light source to collect crystal diffraction data. In the structure analysis, the Shelextl-97 program is used to directly analyze and refine the crystal structure. At the same time, the parameters of non-hydrogen atoms and their anisotropic treatment are corrected using the full matrix least squares method. All hydrogen atoms are obtained by theoretical hydrogenation. The obtained crystal structure is as Figure 1 shown. Each C 44 H 52 Mo 12 N8O 48 Si compound's independent structural unit contains one silicomolybdic acid SiMo 12 O 40 4- anion and two protonated H2NDIDMA 2+ cations, which are interconnected by electrostatic forces and supramolecular forces such as hydrogen bonds, π-π interactions, anion-π interactions, etc. to form a three-dimensional supramolecular structure. Some crystallographic data and refinement parameters are shown in Table 1.

[0031] Table 1 Crystallographic data and refinement parameter table

[0032]

[0033] R1 = ∑││F0│ - │Fc ││ / ∑│F0│.wR2 = {∑[w(F0 2 -F c ) 2 / ∑[w(F0 2 ) 2} 1 / 2 .

[0034] (2) UV absorption spectrum characterization:

[0035] The prepared light absorption material appears black in appearance, as Figure 2 shown. As Figure 3 shown, the UV absorption spectrum of the compound shows strong broadband absorption peaks at 200 - 2500 nm, mainly attributed to the π-π* electronic transition of the ligand itself and the transfer of electrons from silicomolybdic acid to the naphthalenediimide organic group, generating naphthalenediimide radicals.

[0036] (3) Powder diffraction characterization:

[0037] Take an appropriate amount of the single crystal prepared above, grind it fully into powder, place it at room temperature for 3 months, and measure the powder diffraction pattern of the crystal material at room temperature. As Figure 4 shown, by comparing with the diffraction peaks simulated according to the single crystal diffraction data, it can be seen that the experimental measurement results are in good agreement with the fitting results of the Mercury software. Thus, it can be shown that the compound is a pure phase and has good stability under environmental conditions. The anisotropy of the crystal leads to some differences in the peak intensity of some diffraction peaks. At the same time, before and after illumination, the powder diffraction pattern of the powder does not change, proving that the crystal material has good light stability.

[0038] (4) Infrared absorption spectrum characterization:

[0039] Irradiate a beam of infrared rays with different wavelengths onto the molecules of the substance, and certain specific wavelengths of infrared rays are absorbed, forming the infrared absorption spectrum of this molecule. As Figure 5 shown, before and after illumination, the infrared spectrum does not change, indicating that the crystal material has not undergone structural changes and has good light stability.

[0040] The above are only the preferred embodiments of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope covered by the present invention.

Claims

1. An organic-inorganic hybrid light absorption material, characterized in that, It uses N,N'-bis(N,N-dimethylaminoethyl)-1,4,5,8-naphthalenediimide as the organic unit and silicomolybdic acid [SiMo 12 O 40 4- anion as the inorganic unit, which is combined by electrostatic force and supramolecular force; the molecular formula of the light absorption material is C 44 H 52 Mo 12 N8O 48 Si.​ 2. The organic-inorganic hybrid light absorption material according to claim 1, wherein The molecular weight of the light absorption material is 2640.

29. It is a monoclinic single crystal with a space group of P21 / c and the unit cell parameters are as follows: α = 90°, β = 95.849(7)°, γ = 90°, Z = 4.

3. A method for preparing an organic-inorganic hybrid light absorption material as described in any one of claims 1 or 2, characterized in that, It includes the following steps: Slowly drip the mixed solution of dimethylformamide / methanol onto the dimethylformamide solution containing hydroiodic acid and N,N'-bis(N,N-dimethylamino)-1,4,5,8-naphthalenedicarboximide to form a layer separation; then continue to slowly drip the methanol solution containing silicomolybdic acid onto the mixed solution of dimethylformamide / acetonitrile to form a layer separation; after standing in the dark, the organic-inorganic hybrid light absorption material is obtained.

4. The preparation method of the organic-inorganic hybrid light absorption material according to claim 3, wherein In the mixed solution of dimethylformamide / methanol, the volume ratio of dimethylformamide to methanol is 1:

1.

5. The preparation method of the organic-inorganic hybrid light absorption material according to claim 3, wherein, The hydroiodic acid is an aqueous solution with a concentration of 55%.

6. The preparation method of the organic-inorganic hybrid light absorption material according to claim 3, characterized in that, In the dimethylformamide solution containing hydroiodic acid and N,N'-bis(N,N-dimethylamino)-1,4,5,8-naphthalenedicarboximide, the content of N,N'-bis(N,N-dimethylamino)-1,4,5,8-naphthalenedicarboximide is 0.012 mmol / mL, and the content of hydroiodic acid is 0.02 mL / mL.

7. The preparation method of the organic-inorganic hybrid light absorption material according to claim 3, characterized in that, In the methanol solution containing silicomolybdic acid, the content of silicomolybdic acid is 0.006 mmol / mL.

8. The preparation method of the organic-inorganic hybrid light absorption material according to claim 3, wherein, The volume ratio of the methanol solution containing silicomolybdic acid, the mixed solution of dimethylformamide / methanol, and the dimethylformamide solution containing hydroiodic acid and N,N'-bis(N,N-dimethylamino)-1,4,5,8-naphthalenedicarboximide used is 5:1:

5.

9. The preparation method of the organic-inorganic hybrid light absorption material according to claim 3, wherein, The standing time in the dark is 5 days.

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