A zinc complex semiconductor crystal material, a preparation method and use thereof

Abstract

The application discloses a zinc complex semiconductor crystal material with a photocurrent response and a preparation method and application thereof. 82 H 54 N4O 10 S4Zn, a molecular weight is 1449.02, a cell parameter alpha is 71.741(2)°, beta is 78.251(2)°, gamma is 79.792(2)°; the prepared material has a clear space structure and an accurate molecular formula, as a photocurrent response semiconductor material, the material has good redox performance and photocurrent response performance at room temperature, and has a wide application prospect. The technology has the advantages of simple operation, low cost, stable performance, suitability for scale production and the like.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor crystal material chemistry, specifically relating to a zinc complex semiconductor crystal material, its preparation method, and its applications. Background Technology

[0002] Metal coordination compound crystal materials, also known as metal-organic frameworks (MOFs), are organic-inorganic hybrid materials that form intramolecular pores through the self-assembly of organic ligands and metal ions or clusters via coordination bonds. MOFs possess unique characteristics such as high porosity and specific surface area, structural and functional diversity, and unsaturated metal sites. These properties make MOFs a unique type of functional porous material. MOF materials have been widely used in gas adsorption and separation, catalysis, and ion transport.

[0003] Tetrathiafulvalene (TTF) is a stable and reversible two-electron donor. With appropriate potential control, TTF can exist as neutral molecules, radical cations, and divalent cations. To enhance the electron-donating ability of TTF and expand its applications, many TTF derivatives with extended conjugated π groups have been designed and synthesized. These derivatives not only form stable oxidized states and polycations but also allow for smaller HOMO and LUMO orbital gaps, resulting in stronger electron-donating capabilities. The active sites of tetrathiafulvalene can be linked to different conjugated groups, such as pyridine, carboxyl, phenylcyano, thiophene, or furan. These groups can coordinate with transition metal ions to prepare MOFs with different structures. Due to differences in structure, coordinating functional groups, and metal ions, MOFs exhibit different physicochemical properties. Summary of the Invention

[0004] This invention addresses the problems existing in the prior art by providing a zinc complex semiconductor crystal material, its preparation method, and its applications.

[0005] The technical solution adopted by this invention to solve the above-mentioned technical problems is as follows: a zinc complex semiconductor crystal material named NT-MOF1, which belongs to the triclinic crystal system, has a space group of P-1, and a molecular formula of C. 82 H 54 N4O 10 S4Zn, with a molecular weight of 1449.02, has the following unit cell parameters: α=71.741(2)°, β=78.251(2)°, γ=79.792(2)°; Figure 1The results show that the basic unit of NT-MOF1 crystal consists of an m-H4TTFTB ligand, a coordinated 9,10-bis(4-pyridyl)anthracene ligand, a guest 9,10-bis(4-pyridyl)anthracene ligand, two coordinated water molecules, and a Zn atom. 2+ Ionic composition; Zn 2+ The ion center adopts a six-coordinate mode, with two oxygen atoms from the m-H4TTFTB ligand, two oxygen atoms from coordinated water molecules, and two nitrogen atoms from the 9,10-bis(4-pyridyl)anthracene ligand; hydrogen bonds Zinc ions are linked alternately with ligand 9,10-bis(4-pyridyl)anthracene and m-H4TTFTB in different directions to form a two-dimensional planar structure. Figure 2 Two-dimensional planar structures form three-dimensional network structures with channels through hydrogen bonds and intermolecular forces. Figure 3 The guest molecule 9,10-bis(4-pyridyl)anthracene is located in the channels of the three-dimensional network.

[0006] The present invention also provides a method for preparing the semiconductor crystal material, the method comprising the following steps:

[0007] A certain amount of 9,10-bis(4-pyridyl)anthracene, m-H4TTFTB, and zinc salt were weighed and placed in a 20 mL glass bottle. DMF and ethanol were then added to the glass bottle to form a mixed solution. The mixed solution was ultrasonically stirred for 15 min, transferred to a clean glass bottle, and one drop of 2 mol / L HNO3 was added using a pipette. The glass bottle was then placed in an oven and heated at a constant temperature of 70–90 °C for four days. After cooling to room temperature, red blocky crystals precipitated in the glass bottle. The solution was filtered, washed with DMF and ethanol, and then dried at room temperature to obtain dry red blocky crystals with photocurrent response properties, which is the zinc complex semiconductor crystal material described above.

[0008] The zinc salt may be one or more of zinc nitrate, zinc acetate, and zinc sulfate;

[0009] The molar ratio of the ligand 9,10-bis(4-pyridyl)anthracene, m-H4TTFTB and zinc salt is 1:1:2;

[0010] The ligand 9,10-bis(4-pyridyl)anthracene has the structural formula shown in Formula (I):

[0011]

[0012] The ligand m-H4TTFTB has the following simplified structural formula (II):

[0013]

[0014] All substances or solvents participating in the reaction are chemically pure.

[0015] The present invention also provides the use of the zinc complex semiconductor crystal material, which, as a photocurrent-responsive metal-organic framework material, exhibits good redox properties and photocurrent response properties at room temperature and has broad application prospects.

[0016] Compared with the prior art, the present invention is characterized by:

[0017] The 9,10-bis(4-pyridyl)anthracene structural unit has a 26-center, 28-electron large conjugated unit π. 26 28 The tetrathiofulvalene structural unit has a 10-center, 14-electron large conjugated unit π. 10 14 When a tetrathiofulvalene unit is attached to four carboxybenzene units, a larger conjugated unit is formed. These two ligands with large conjugated units, together with zinc ions, form zinc complex crystals with specific structures and specific conjugated units, giving the crystal material specific redox properties. Furthermore, both anthracene and tetrathiofulvalene derivatives exhibit good electrical conductivity. The zinc complex semiconductor crystal material prepared in this invention possesses unique photocurrent response properties, with a relative photocurrent intensity of approximately 0.72 μA·cm. -1 It has broad application prospects as a semiconductor crystal material. Attached Figure Description

[0018] Figure 1 This is the basic structural unit of the NT-MOF1 of the present invention;

[0019] Figure 2 This is the two-dimensional planar structure of the NT-MOF1 of the present invention;

[0020] Figure 3 This is a three-dimensional packing diagram of NT-MOF1 of the present invention. To show the pore structure, the 9,10-bis(4-pyridyl)anthracene ligand of the guest molecule is omitted.

[0021] Figure 4 Thermogravimetric spectrum of NT-MOF1 of the present invention;

[0022] Figure 5 This is the cyclic voltammetry spectrum of the NT-MOF1 of the present invention;

[0023] Figure 6 This is the photocurrent response spectrum of the NT-MOF1 of the present invention. Detailed Implementation

[0024] The present invention will be further described in detail below with reference to the embodiments.

[0025] Example 1:

[0026] Weigh 0.033 g (0.1 mmol) of 9,10-bis(4-pyridyl)anthracene, 0.068 g (0.1 mmol) of m-H4TTFTB, and 0.076 g (0.2 mmol) of Zn(NO3)2·6H2O into a 20 mL glass bottle. Then add 4.0 mL of DMF and 1.0 mL of ethanol to the glass bottle to form a mixture solution. Stir the mixture solution ultrasonically for 15 min and add one drop of 2 mol / L HNO3 with a pipette. Then place the glass bottle in an oven and heat it at 90 °C for four days. After cooling to room temperature, red blocky crystals precipitate in the glass bottle. Filter the solution, wash it with DMF and ethanol, and then dry it at room temperature to obtain dry red blocky crystals.

[0027] Example 2:

[0028] Weigh 0.066 g (0.2 mmol) of 9,10-bis(4-pyridyl)anthracene, 0.136 g (0.2 mmol) of m-H4TTFTB, and 0.88 g (0.4 mmol) of zinc acetate (CH3COO)2Zn·2H2O) into a 20 mL glass bottle. Then add 8.0 mL of DMF and 2.0 mL of ethanol to the glass bottle to form a mixture solution. Stir the mixture solution ultrasonically for 15 min and add one drop of 2 mol / L HNO3 with a pipette. Then place the glass bottle in an oven and heat it at 70 °C for four days. After cooling to room temperature, red blocky crystals precipitate in the glass bottle. Filter the solution, wash it with DMF and ethanol, and then dry it at room temperature to obtain dry red blocky crystals.

[0029] Example 3:

[0030] Weigh 0.0165 g (0.05 mmol) of 9,10-bis(4-pyridyl)anthracene, 0.034 g (0.05 mmol) of m-H4TTFTB, and 0.029 g (0.1 mmol) of ZnSO4·7H2O into a 20 mL glass bottle. Then add 4.0 mL of DMF and 4.0 mL of ethanol to the glass bottle to form a mixture solution. Stir the mixture solution ultrasonically for 15 min and add one drop of 2 mol / L HNO3 with a pipette. Then place the glass bottle in an oven and heat it at 80 °C for four days. After cooling to room temperature, red blocky crystals precipitate in the glass bottle. Filter the solution, wash it with DMF and ethanol, and then dry it at room temperature to obtain dry red blocky crystals.

[0031] The red blocky crystals prepared in the above embodiments were subjected to single-crystal X-ray diffraction analysis. Crystals of suitable size and regular shape were selected at room temperature and fixed to the test probe with epoxy resin. The test probe was then placed above the Bruker APEX-II CCD diffraction line, and graphite monochromatic MoKα rays were used for analysis. The samples were tested, and data were acquired using CrysAlis Pro-Agilent software. Diffraction points were screened, lattice type was determined, and absorption correction and data restoration were performed. The crystal structure was solved directly using the ShelXS program, and anisotropic refinement was performed using ShelXL. 2 The structure was refined and corrected using the full matrix least squares method. The coordinates of non-hydrogen atoms in the structure were gradually determined by differential Fourier peak synthesis and anisotropically refined. Hydrogen atoms were obtained through theoretical hydrogenation. All hydrogen atoms underwent isotropic refinement, resulting in a complete CIF file. In the CIF file, the residual factor R1 (R_factor_gt) was 0.0397, the goodness of fit S or GooF (goodness_of_fit_ref) for multiple diffraction points was 1.054, and the average shift value (shift / su_mean) during the final refinement process was 0.000. These parameters already meet the precise data requirements for crystal structure analysis as required by crystallography. X-ray single-crystal diffraction analysis showed that NT-MOF1 belongs to the triclinic crystal system, space group P-1, and molecular formula C. 82 H 54 N4O 10 S4Zn, with a molecular weight of 1449.02, has the following unit cell parameters: α=71.741(2)°, β=78.251(2)°, γ=79.792(2)°; The basic unit of crystal NT-MOF1 consists of an m-H4TTFTB ligand, a coordinated 9,10-bis(4-pyridyl)anthracene ligand, a guest 9,10-bis(4-pyridyl)anthracene ligand, two coordinated water molecules, and a Zn 2+ Ionic composition; Zn 2+ The ion center adopts a six-coordinate mode, with two oxygen atoms from the m-H4TTFTB ligand, two oxygen atoms from coordinated water molecules, and two nitrogen atoms from the 9,10-bis(4-pyridyl)anthracene ligand; hydrogen bonds Zinc ions are alternately linked with ligand 9,10-bis(4-pyridyl)anthracene and m-H4TTFTB in different directions to form a two-dimensional planar structure. This two-dimensional planar structure forms a porous three-dimensional network structure through hydrogen bonds and intermolecular forces, with the guest molecule 9,10-bis(4-pyridyl)anthracene located within the channels of this three-dimensional network. Test results show that the red, bulky crystals prepared in the examples are indeed the zinc complex semiconductor crystal material described above.

[0032] Figure 1 The basic structural unit of the zinc complex semiconductor crystal material of NT-MOF1; Figure 2 The two-dimensional planar structure of the zinc complex semiconductor crystal material of NT-MOF1; Figure 3 The three-dimensional stacking of the zinc complex semiconductor crystal material of NT-MOF1 is shown. The 9,10-bis(4-pyridyl)anthracene ligand of the guest molecule is omitted to show the pore structure.

[0033] The crystals prepared above were subjected to thermogravimetric analysis. Figure 4 The results showed that the MOF framework could remain stable at around 400℃, indicating that the crystal had good thermal stability.

[0034] Electrochemical cyclic voltammetry (CV) performance testing Figure 5 The ligand and product crystal were dissolved separately in 2 mL of DMF solution, and then 2 mL of DMF solution containing tetrabutylammonium perchlorate (0.1 mol / L) was added (V:V = 1:1). After thorough mixing, cyclic voltammetry was performed on a CHI660E electrochemical workstation using a three-electrode system (glass electrode as working electrode, platinum electrode (Pt) as auxiliary electrode, and saturated calomel electrode (SCE) as reference electrode) at a scan rate of 50 mV / s. For the product crystal, the potentials of the two oxidation peaks were more negative than those of the ligand m-H4TTFTB, indicating that the electron density of the product crystal was higher than that of the ligand m-H4TTFTB. This indicates that the product crystal had a higher electron density than the ligand m-H4TTFTB, which affected the overall electrochemical properties of the compound and lowered the first oxidation potential of the ligand, making it easier to be oxidized. This result shows that the structure of the product crystal has specific redox properties (Table 1), which has an important influence on its conductivity.

[0035] Table 1. Oxidation potentials of ligand m-H4TTFTB and product crystals.

[0036]

[0037] Photocurrent response performance test ( Figure 65 mg of the product crystals were weighed and dispersed in a mixed solution of 200 μL ethanol and 10 μL nafion (perfluorosulfonic acid polymer solution), and ultrasonically dispersed to ensure uniform dispersion. The uniformly dispersed suspension was dropped onto a 1.0 cm × 1.0 cm ITO conductive glass plate and dried in air to obtain the working electrode. Using 0.1 mol / L sodium sulfate solution as the electrolyte, a three-electrode system was used (the ITO conductive glass electrode coated with the sample as the working electrode, the platinum electrode (Pt) as the auxiliary electrode, and the saturated calomel electrode (SCE) as the reference electrode). The test was conducted in a CH1660E electrochemical workstation using a high-pressure mercury lamp (150 W) as the light source. The distance between the light source and the ITO glass electrode was 20 cm. The initial voltage of the test was 0.6 V, and the light source was controlled by a light shield, with a time interval of 20 s. At room temperature, a stable photocurrent signal is immediately obtained when illuminated by a light source. When the light source is blocked, the photocurrent immediately drops back to its initial position. This cycle repeats, resulting in a stable photocurrent signal with a relative intensity of approximately 0.72 μA·cm. -1 This indicates that the product is stable, does not easily decompose in solution, and has good photocurrent response performance at room temperature, suggesting that it has broad application prospects as a photocurrent-responsive semiconductor crystal material.

Claims

1. A zinc complex semiconductor crystal material, characterized in that, The zinc complex semiconductor crystal material is named NT-MOF1. This semiconductor crystal material belongs to the triclinic crystal system and has a space group of [missing information]. P -1, molecular formula is C 82 H 54 N4O 10 S4Zn, with a molecular weight of 1449.02, has unit cell parameters a = 10.491(4) Å, b = 13.027(5) Å, and c = 13.715(5) Å. α =71.741(2)°, β =78.251(2)°, γ = 79.792(2)°; its basic unit consists of one m The ligand consists of -H4TTFTB, a coordinated 9,10-bis(4-pyridyl)anthracene ligand, a guest 9,10-bis(4-pyridyl)anthracene ligand, two coordinated water molecules, and a Zn. 2+ Ionic composition; Zn 2+ The ion center adopts a six-coordinate mode, in which two oxygen atoms come from... m The -H4TTFTB ligand, with two oxygen atoms from coordinated water molecules, and two nitrogen atoms from the coordinated 9,10-bis(4-pyridyl)anthracene ligand; hydrogen bonds O3-H5A···O5 = 2.667 Å, ​​N2-H5B···O5 = 2.087 Å; zinc ions are bonded via the coordinated 9,10-bis(4-pyridyl)anthracene ligand. m -H4TTFTB molecules are alternately linked in different directions to form a two-dimensional planar structure; the two-dimensional planar structure forms a three-dimensional network structure with channels through hydrogen bonds and intermolecular forces, and the guest molecule 9,10-bis(4-pyridyl)anthracene is located in the channels of the three-dimensional network; The 9,10-bis(4-pyridyl)anthracene ligand has the structural formula shown in Formula (I): Equation (I); The m The structural formula of the -H4TTFTB ligand is shown in equation (II) below: Formula (II).

2. A method for preparing a zinc complex semiconductor crystal material as described in claim 1, characterized in that, The preparation method includes the following steps: Weigh a certain amount of 9,10-bis(4-pyridyl)anthracene, m -H4TTFTB and zinc salt were placed in a 20 mL glass bottle, and then DMF and ethanol were added to the glass bottle to form a mixture solution. The mixture solution was ultrasonically stirred for 15 min, transferred to a clean glass bottle, and a drop of 2 mol / L HNO3 was added with a pipette. The glass bottle was then placed in an oven and heated at a constant temperature of 70~90 ℃ for four days. After cooling to room temperature, red blocky crystals precipitated in the glass bottle. The solution was filtered, washed successively with DMF and ethanol, and then dried at room temperature to obtain dry red blocky crystals with photocurrent response. The red blocky crystals are a zinc complex semiconductor crystal material. The zinc salt may be one or more of zinc nitrate, zinc acetate, and zinc sulfate; The ligand 9,10-bis(4-pyridyl)anthracene, m The molar ratio of -H4TTFTB to zinc salt is 1:1:2; All substances or solvents participating in the reaction are chemically pure.

3. The use of the zinc complex semiconductor crystal material according to claim 1, characterized in that, At room temperature, this crystalline material exhibits good redox properties and photocurrent response properties, and as a photocurrent-responsive semiconductor material, it has broad application prospects.

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