Single-crystal 1, 4-diaminobutane cadmium halide crystal as well as preparation and application thereof
By preparing single crystal 1,4-diaminobutanyl cadmium halide crystals and combining the interlaced structure of organic ammonium cations and inorganic octahedrals, the problem of insufficient application of organic inorganic hybrid materials in the prior art in ultra-wide bandgap semiconductors has been solved, efficient photoelectric properties and stable material properties have been achieved, and its application in the fields of photodetectors, data storage and photovoltaics has been expanded.
Patent Information
- Application Number
- CN202510494985.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-21
- Publication Date
- 2025-07-22
AI Technical Summary
The prior art has mainly focused on inorganic materials in the research of ultra-wide bandgap semiconductor materials. The lack of research on organic and inorganic hybrid materials has led to the inadequate use of the material's ease of modification, structural diversity and bandgap tunability, which limits its application potential in the fields of photodetectors, data storage and photovoltaics.
Single crystal 1,4-diaminobutanyl cadmium halide crystals were prepared, and a two-dimensional layered or one-dimensional branched chain structure with infinitely intersected CdX6 octahedral and (C4N2H14)2+ cation layer was formed, and the synthesis was performed by gentle and simple hydrothermal method.
It improves carrier mobility, gives single crystal unique optical, electrical and photoelectric characteristics, and expands its application prospects in the fields of photodetectors, data storage and photovoltaics. It has stable material properties and regular morphology, and its bandwidth is surpassed by traditional wide bandgap semiconductors.
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Figure CN120350435A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of organic-inorganic technology, and particularly to a single-crystal 1,4-diaminobutane cadmium halide crystal and its preparation and application. Background Art
[0002] Due to their remarkable material properties, such as high breakdown voltage, low power consumption, and good thermal stability, ultra-wide bandgap semiconductors are becoming a research hotspot. For example, the ultra-wide energy gap (4.8 eV) and high critical breakdown field strength (8 MV / cm) of gallium oxide (Ga2O3) enable it to exhibit excellent performance in high-voltage power electronic devices, far exceeding those of traditional silicon (Si), silicon carbide (SiC), and gallium nitride (GaN). These properties not only enhance the voltage withstand capacity and efficiency of the devices but also enable them to operate stably at higher temperatures and in more severe environments.
[0003] Currently, although the research on ultra-wide bandgap semiconductors mainly focuses on inorganic materials, organic-inorganic hybrid materials show great potential due to their unique easy modifiability, structural diversity, and bandgap tunability. Such materials are not only of great significance in basic scientific research but also provide new possibilities in the development and application of new technologies. For example, by designing new structures and synthesis methods, high-crystallinity and high-purity organic-inorganic hybrid single crystals can be prepared to optimize their optoelectronic properties.
[0004] Research on ultra-wide bandgap semiconductors not only holds the promise of breakthroughs in existing technologies but also may open up entirely new application fields. From power electronics to optoelectronic devices and then to electronic devices in radiation environments, the application prospects of these materials are broad. Especially for modern electronic devices that require high efficiency and low energy consumption, the application of ultra-wide bandgap semiconductors will greatly promote technological progress and meet the growing demand of the electronic device market.
[0005] Therefore, whether from the perspective of basic scientific research or applied technology, researching ultra-wide bandgap semiconductors is of profound significance and great value. Summary of the Invention
[0006] To solve the above problems, the purpose of the present invention is to provide a single-crystal 1,4-diaminobutane cadmium halide crystal and its preparation and application.
[0007] The purpose of the present invention can be achieved by the following technical solutions:
[0008] The first purpose of the present invention is to provide a single-crystal 1,4-diaminobutane cadmium halide crystal with the chemical formula C4N2H 14 CdX4; X is one of Cl, Br, or I;
[0009] In the single-crystal 1,4-diaminobutane cadmium halide crystal, the central Cd2+ The cation coordinates with four individual and two adjacent bridging X - anions to form a CdX6 octahedron. The CdX6 octahedron layers and (C4N2H 14 ) 2+ cation layers interleave infinitely to form a two-dimensional layered structure or a one-dimensional branched chain-like structure.
[0010] In one embodiment of the present invention, when X is Cl, the unit cell parameters of the single crystal 1,4-diaminobutane cadmium chloride crystal are and α = 90°, β = 101.586(7)°, γ = 90°.
[0011] In one embodiment of the present invention, when X is Br, the unit cell parameters of the single crystal 1,4-diaminobutane cadmium chloride crystal are and α = 90°, β = 94.813(10)°, γ = 90°.
[0012] The present invention combines organic ammonium cations with inorganic octahedrons, which can not only improve the carrier mobility, but also endow the single crystal 1,4-diaminobutane cadmium halide crystal with unique optical, electrical, and optoelectronic properties to achieve excellent performance.
[0013] The second object of the present invention is to provide a method for preparing a single crystal 1,4-diaminobutane cadmium halide crystal, comprising the following steps:
[0014] (S1) Dissolve cadmium carbonate in hydrogen halide to obtain a cadmium carbonate solution;
[0015] (S2) Mix the cadmium carbonate solution prepared in step (S1) with 1,4-diaminobutane and carry out a hydrothermal reaction, and then perform post-treatment to obtain a single crystal 1,4-diaminobutane cadmium halide crystal;
[0016] In one embodiment of the present invention, in step (S1), the hydrogen halide is selected from one of HCl, HBr, or HI.
[0017] In one embodiment of the present invention, in step (S1), the dosage ratio of cadmium carbonate to hydrogen halide is 0.01 mol: 25 - 30 mL;
[0018] Preferably, in step (S1), the dosage ratio of cadmium carbonate to hydrogen halide is 0.01 mol: 25 mL;
[0019] In one embodiment of the present invention, in step (S2), the molar ratio of the cadmium carbonate solution to 1,4-diaminobutane is 1: 0.5 - 1.5;
[0020] Preferably, the molar ratio of cadmium carbonate solution to 1,4-diaminobutane is 1:1;
[0021] In one embodiment of the present invention, in step (S2), during the hydrothermal reaction, the temperature is 120 - 180 °C and the time is 10 - 14 h;
[0022] Preferably, during the hydrothermal reaction, the temperature is 120 °C and the time is 10 h.
[0023] In one embodiment of the present invention, in step (S2), the post-treatment is specifically to collect the precipitate obtained from the reaction after the reaction ends, wash the precipitate, and then dry it.
[0024] The third object of the present invention is to provide an application of a single crystal 1,4-diaminobutane cadmium halide crystal in photodetectors, data storage, and the photovoltaic field.
[0025] Compared with the prior art, the present invention has the following beneficial effects:
[0026] (1) The 1,4-diaminobutane cadmium halide crystal provided by the present invention has a clear crystal structure. The CdX6 octahedral layer (X is one of F, Cl, Br, I, or At) and the (C4N2H 14 ) 2+ cation layers are infinitely interleaved to form a two-dimensional layered structure or a one-dimensional branched chain-like structure, with stable properties and unique single crystal spectrum information, which has a more definite directivity for studying the properties of the 1,4-diaminobutane cadmium halide crystal; moreover, the 1,4-diaminobutane cadmium halide crystal provided by the present invention has an ultra-wide bandgap and has broad application prospects in fields such as photodetectors, data storage, and photovoltaics.
[0027] (2) The present invention uses a mild and simple hydrothermal method to prepare the 1,4-diaminobutane cadmium halide crystal. The samples prepared by the hydrothermal method have good quality and relatively regular morphologies. Description of the Drawings
[0028] Figure 1 is the XRD pattern of the 1,4-diaminobutane cadmium chloride crystal in Example 1;
[0029] Figure 2 is the structure diagram of the 1,4-diaminobutane cadmium chloride crystal in Example 1;
[0030] Figure 3 is the optical micrograph of the 1,4-diaminobutane cadmium chloride crystal in Example 1;
[0031] Figure 4 is the ultraviolet-visible absorption spectrum and its bandgap diagram of the 1,4-diaminobutane cadmium chloride crystal in Example 1;
[0032] Figure 5 is the XRD pattern of the 1,4-diaminobutane cadmium bromide crystal in Example 4;
[0033] Figure 6 is the structural diagram of the 1,4-diaminobutane cadmium bromide crystal in Example 4;
[0034] Figure 7 is the optical micrograph of the 1,4-diaminobutane cadmium bromide crystal in Example 4;
[0035] Figure 8 is the ultraviolet-visible absorption spectrum and its band gap diagram of the 1,4-diaminobutane cadmium bromide crystal in Example 4. Detailed implementation mode
[0036] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
[0037] The present invention provides a single crystal 1,4-diaminobutane cadmium halide crystal, the chemical formula of which is C4N2H 14 CdX4; X is one of Cl, Br or I;
[0038] In the single crystal 1,4-diaminobutane cadmium halide crystal, the central Cd 2+ cation coordinates with four individual and two adjacent bridging X - anions to form a CdX6 octahedron, and the CdX6 octahedron layers and (C4N2H 14 ) 2+ cation layers are infinitely interleaved to form a two-dimensional layered structure or a one-dimensional branched chain-like structure.
[0039] Furthermore, when X is Cl, the unit cell parameters of the single crystal 1,4-diaminobutane cadmium chloride crystal are and α = 90°, β = 101.586(7)°, γ = 90°.
[0040] Furthermore, when X is Br, the unit cell parameters of the single crystal 1,4-diaminobutane cadmium chloride crystal are and α = 90°, β = 94.813(10)°, γ = 90°.
[0041] The present invention combines organic ammonium cations with inorganic octahedrons, which can not only improve the carrier mobility, but also endow the single crystal 1,4-diaminobutane cadmium halide crystal with unique optical, electrical and optoelectronic properties, so as to achieve excellent performance.
[0042] The present invention provides a preparation method of a single crystal 1,4-diaminobutane cadmium halide crystal, comprising the following steps:
[0043] (S1) Dissolve cadmium carbonate in hydrogen halide to obtain a cadmium carbonate solution;
[0044] (S2) Mix the cadmium carbonate solution prepared in step (S1) with 1,4-diaminobutane and carry out a hydrothermal reaction, followed by post-treatment to obtain single-crystal 1,4-diaminobutane cadmium halide crystals;
[0045] Further, in step (S1), the hydrogen halide is selected from one of HCl, HBr or HI.
[0046] Further, in step (S1), the dosage ratio of cadmium carbonate to hydrogen halide is 0.01 mol: 25 - 30 mL;
[0047] Preferably, in step (S1), the dosage ratio of cadmium carbonate to hydrogen halide is 0.01 mol: 25 mL;
[0048] Further, in step (S2), the molar ratio of the cadmium carbonate solution to 1,4-diaminobutane is 1: 0.5 - 1.5;
[0049] Preferably, the molar ratio of the cadmium carbonate solution to 1,4-diaminobutane is 1: 1;
[0050] Further, in step (S2), during the hydrothermal reaction, the temperature is 120 - 180 °C and the time is 10 - 14 h;
[0051] Preferably, during the hydrothermal reaction, the temperature is 120 °C and the time is 10 h.
[0052] Further, in step (S2), the post-treatment is specifically to collect the precipitate obtained from the reaction after the reaction ends, wash the precipitate and then dry it.
[0053] The present invention provides an application of single-crystal 1,4-diaminobutane cadmium halide crystals in photodetectors, data storage, and the photovoltaic field.
[0054] In the following examples, the mass fraction of hydrochloric acid is 36%; the mass fraction of hydrobromic acid is 50%; unless otherwise specified, all reagents used are commercially available reagents, and all detection means and methods used are conventional detection means and methods in the art.
[0055] Example 1
[0056] This example provides a preparation method (hydrothermal synthesis method) of single-crystal 1,4-diaminobutane cadmium chloride crystals, which specifically includes the following steps:
[0057] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrochloric acid, mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0058] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture.
[0059] (S3) Transfer the mixture prepared in step (S2) into the inner lining of a 50 mL reaction kettle, load the kettle (lay flat and tighten), react in an oven at 120 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure.
[0060] After the reaction kettle is cooled and the pressure is relieved, slowly pour out the supernatant liquid therein and retain the white precipitate; use a disposable pipette to assist in transferring the white precipitate into a 50 mL large centrifuge tube, and use a pipette to suck ethyl acetate (30 mL) to centrifuge and wash the crystal sample; centrifuge the white precipitate repeatedly 5 times, pour out the upper layer liquid after each centrifugation and retain the precipitate, then repeat the above operation to add ethyl acetate to continue washing until the solvent is transparent after centrifugation to obtain a washed white precipitate, and then place it in a drying oven at 60 °C to dry to prepare 1,4-diaminobutane cadmium chloride crystals.
[0061] After testing, the size of the single crystal product is about 120 microns, and the chemical formula of the single crystal 1,4-diaminobutane cadmium chloride crystal is C4N2H 14 CdCl4.
[0062] Example 2
[0063] This example provides a method for preparing single crystal 1,4-diaminobutane cadmium chloride crystals (hydrothermal synthesis method), which specifically includes the following steps:
[0064] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrochloric acid, and mix well by magnetic stirring to obtain a cadmium carbonate solution.
[0065] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture.
[0066] (S3) Transfer the mixture prepared in step (S2) into the inner lining of a 50 mL reaction kettle, load the kettle (lay flat and tighten), react in an oven at 150 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure.
[0067] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was sucked with a pipette to centrifuge and wash the crystal sample. The white precipitate was centrifuged 5 times repeatedly. After each centrifugation, the upper layer liquid was poured out, and the precipitate was retained. Then, the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation. The washed white precipitate was obtained and then dried in an oven at 60 °C to prepare 1,4-diaminobutane cadmium chloride crystals.
[0068] After testing, the size of the single crystal product was about 150 microns, and the chemical formula of the single crystal 1,4-diaminobutane cadmium chloride crystal was C4N2H 14 CdCl4.
[0069] Example 3
[0070] This example provides a preparation method (hydrothermal synthesis method) of single crystal 1,4-diaminobutane cadmium chloride crystals, which specifically includes the following steps:
[0071] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrochloric acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0072] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixed solution;
[0073] (S3) Load the mixed solution prepared in step (S2) into the inner lining of a 50 mL reactor, install the reactor (place it flat and tighten it), react in an oven at 180 °C for 12 h, then cool the reactor to room temperature and depressurize it;
[0074] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was sucked with a pipette to centrifuge and wash the crystal sample. The white precipitate was centrifuged 5 times repeatedly. After each centrifugation, the upper layer liquid was poured out, and the precipitate was retained. Then, the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation. The washed white precipitate was obtained and then dried in an oven at 60 °C to prepare 1,4-diaminobutane cadmium chloride crystals.
[0075] After testing, the size of the single crystal product was about 200 microns, and the chemical formula of the single crystal 1,4-diaminobutane cadmium chloride crystal was C4N2H 14 CdCl4.
[0076] Performance test:
[0077] At 296 K, the crystal data of the white single crystal obtained in Example 1 was collected using a Bruker D8 single crystal diffractometer in ω-scan mode under Mo-Kα (λ = 0.71073 Å) radiation. As shown in Table 1, the crystal is monoclinic, with the space group P21 / c, and α = 90°, β = 101.586(7)°, γ = 90°; Z = 2,
[0078] Table 1 Crystal parameters of cadmium chloride 1,4-diaminobutane single crystal
[0079]
[0080]
[0081] The cadmium chloride 1,4-diaminobutane crystal prepared in Example 1 was detected using an X-ray diffractometer, and its XRD pattern is as Figure 1 shown. The experimentally obtained XRD pattern is in good agreement with the simulated data based on the crystal structure, indicating that the obtained sample is a pure phase and has a high crystallinity. Structurally, the central Cd 2+ cation coordinates with four individual and two adjacent bridging Cl - anions to form a CdCl6 octahedron. The CdCl6 octahedron layers and the (C4N2H 14 ) 2+ cation layers are infinitely interleaved to form a two-dimensional layered structure (as Figure 2 shown).
[0082] The crystal morphology of the white transparent single crystal obtained in Example 1 was characterized, and the sample has a regular polyhedral morphology (as Figure 3 shown).
[0083] The ultraviolet-visible absorption spectrum and its band gap diagram of the cadmium chloride 1,4-diaminobutane crystal prepared in Example 1 are as Figure 4 shown. It can be found through Figure 4 that the band gap of the cadmium chloride 1,4-diaminobutane crystal is 5.17 eV, and its band gap exceeds that of traditional wide-bandgap semiconductors (such as GaN, SiC). Combining the high stability of the inorganic phase and the tunability of the organic components of the material, the energy band engineering is optimized through hybrid design, showing significant potential in the fields of ultraviolet detection, sterilization and disinfection, high-density optical storage, etc. At the application level, this material may contribute to the technological innovation of deep ultraviolet optoelectronic devices (sterilization, lithography, environmental sensing), high-temperature / high-pressure power electronics (new energy, smart grid), and radiation-resistant devices (space, nuclear industry).
[0084] Example 4
[0085] This embodiment provides a method for preparing a single crystal of 1,4-diaminobutane cadmium bromide (hydrothermal synthesis method), which specifically includes the following steps:
[0086] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrobromic acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0087] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture;
[0088] (S3) Pour the mixture prepared in step (S2) into a 50 mL reaction kettle liner, load the kettle (lay flat and tighten), react in an oven at 120 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0089] After the reaction kettle is cooled and the pressure is relieved, slowly pour out the supernatant liquid therein and retain the white precipitate; use a disposable straw to assist in transferring the white precipitate to a 50 mL large centrifuge tube, and use a straw to suck ethyl acetate (30 mL) to centrifuge and wash the crystal sample; centrifuge the white precipitate repeatedly 5 times, pour out the upper layer liquid after each centrifugation, retain the precipitate, and repeat the above operation to add ethyl acetate to continue washing until the solvent is transparent after centrifugation to obtain a washed white precipitate, and then place it in a drying oven at 60 °C to dry to prepare a 1,4-diaminobutane cadmium bromide crystal.
[0090] After testing, the size of the single crystal product is about 120 microns, and the chemical formula of the single crystal 1,4-diaminobutane cadmium bromide crystal is C4N2H 14 CdBr4.
[0091] Example 5
[0092] This embodiment provides a method for preparing a single crystal of 1,4-diaminobutane cadmium bromide (hydrothermal synthesis method), which specifically includes the following steps:
[0093] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrobromic acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0094] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture;
[0095] (S3) Pour the mixture prepared in step (S2) into a 50 mL reaction kettle liner, load the kettle (lay flat and tighten), react in an oven at 150 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0096] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was sucked with the pipette to centrifuge and wash the crystal sample. The white precipitate was centrifuged 5 times repeatedly. After each centrifugation, the upper layer of liquid was poured out, and the precipitate was retained. Then, the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation, and the washed white precipitate was obtained. Then, it was placed in a drying oven and dried at 60 °C to prepare 1,4-diaminobutane cadmium bromide crystals.
[0097] After testing, the size of the single crystal product was about 150 microns, and the chemical formula of the single crystal 1,4-diaminobutane cadmium bromide crystal was C4N2H 14 CdBr4.
[0098] Example 6
[0099] This example provides a preparation method (hydrothermal synthesis method) of single crystal 1,4-diaminobutane cadmium bromide crystals, which specifically includes the following steps:
[0100] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrobromic acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0101] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixed solution;
[0102] (S3) Pour the mixed solution prepared in step (S2) into the inner lining of a 50 mL reactor, load the reactor (place it flat and tighten it), react in an oven at 180 °C for 12 h, then cool the reactor to room temperature and depressurize it;
[0103] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was sucked with the pipette to centrifuge and wash the crystal sample. The white precipitate was centrifuged 5 times repeatedly. After each centrifugation, the upper layer of liquid was poured out, and the precipitate was retained. Then, the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation, and the washed white precipitate was obtained. Then, it was placed in a drying oven and dried at 60 °C to prepare 1,4-diaminobutane cadmium bromide crystals.
[0104] After testing, the size of the single crystal product was about 200 microns, and the chemical formula of the single crystal 1,4-diaminobutane cadmium bromide crystal was C4N2H 14 CdBr4.
[0105] Performance test:
[0106] At 296 K, the crystal data of the white single crystal obtained in Example 4 was collected using a Bruker D8 single crystal diffractometer in ω-scan mode under Mo-Kα (λ = 0.71073 Å) radiation. As shown in Table 2, the crystal is monoclinic, the space group is P21 / c, and α = 90°, β = 94.813(10)°, γ = 90°; Z = 4,
[0107] Table 2 Crystal parameters of cadmium bromide 1,4-diaminobutane single crystal
[0108]
[0109] The cadmium bromide 1,4-diaminobutane crystal prepared in Example 4 was detected using an X-ray diffractometer, and its XRD pattern is as Figure 5 shown. The experimentally obtained XRD pattern is in good agreement with the simulated data based on the crystal structure, indicating that the obtained sample is a pure phase and has a high crystallinity. Structurally, the central Cd 2+ cation coordinates with four individual and two adjacent bridging Br - anions to form a CdBr6 octahedron. The CdBr6 octahedron layers and the (C4N2H 14 ) 2+ cation layers are infinitely interleaved to form a one-dimensional branched chain-like structure (as Figure 6 shown).
[0110] The crystal morphology of the white transparent single crystal obtained in Example 4 was characterized, and the sample has a regular polyhedral morphology (as Figure 7 shown).
[0111] The UV-visible absorption spectrum and its band gap diagram of the cadmium bromide 1,4-diaminobutane crystal prepared in Example 1 are as Figure 8 shown. It can be found through Figure 8 that the band gap of the cadmium bromide 1,4-diaminobutane crystal is 4.33 eV, and its band gap exceeds that of traditional wide band gap semiconductors (such as GaN, SiC). Combining the high stability of the inorganic phase and the tunability of the organic components, the energy band engineering is optimized through hybrid design, and it has significant potential in the fields of ultraviolet detection, sterilization and disinfection, high-density optical storage, etc. At the application level, this material may contribute to the technological innovation of deep ultraviolet optoelectronic devices (sterilization, lithography, environmental sensing), high-temperature / high-pressure power electronics (new energy, smart grid), and radiation-resistant devices (space, nuclear industry).
[0112] Example 7
[0113] This example provides a preparation method (hydrothermal synthesis method) of a single crystal cadmium chloride 1,4-diaminobutane crystal, which specifically includes the following steps:
[0114] (S1) Dissolve 0.01 mol of CdCO3 in 28 mL of hydrochloric acid, mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0115] (S2) Add 0.015 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture;
[0116] (S3) Transfer the mixture prepared in step (S2) into a 50 mL reaction kettle liner, load the kettle (lay flat and tighten), react in an oven at 120 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0117] After the reaction kettle is cooled and the pressure is relieved, slowly pour out the supernatant liquid therein and retain the white precipitate; use a disposable pipette to assist in transferring the white precipitate into a 50 mL large centrifuge tube, and use a pipette to suck ethyl acetate (30 mL) to centrifuge and wash the crystal sample; centrifuge the white precipitate 5 times repeatedly, pour out the upper layer liquid after each centrifugation and retain the precipitate, then repeat the above operation to add ethyl acetate and continue washing until the solvent is transparent after centrifugation to obtain a washed white precipitate, and then place it in a drying oven and dry it at 60 °C to prepare 1,4-diaminobutane cadmium chloride crystals.
[0118] Example 8
[0119] This example provides a method for preparing single crystal 1,4-diaminobutane cadmium chloride crystals (hydrothermal synthesis method), which specifically includes the following steps:
[0120] (S1) Dissolve 0.01 mol of CdCO3 in 30 mL of hydrochloric acid, mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0121] (S2) Add 0.005 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture;
[0122] (S3) Transfer the mixture prepared in step (S2) into a 50 mL reaction kettle liner, load the kettle (lay flat and tighten), react in an oven at 120 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0123] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was pipetted to centrifuge and wash the crystal sample. The white precipitate was centrifuged 5 times repeatedly. After each centrifugation, the upper layer liquid was poured out, and the precipitate was retained. Then the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation, and the washed white precipitate was obtained. Then it was placed in an oven at 60 °C for drying to prepare 1,4-diaminobutane cadmium chloride crystals.
[0124] Example 9
[0125] This example provides a method for preparing single crystal 1,4-diaminobutane cadmium chloride crystals (hydrothermal synthesis method), which specifically includes the following steps:
[0126] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrochloric acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0127] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture;
[0128] (S3) Pour the mixture prepared in step (S2) into the inner lining of a 50 mL reactor, install the reactor (place it flat and tighten it), react in an oven at 140 °C for 14 h, then cool the reactor to room temperature and depressurize it;
[0129] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was pipetted to centrifuge and wash the crystal sample. The white precipitate was centrifuged 5 times repeatedly. After each centrifugation, the upper layer liquid was poured out, and the precipitate was retained. Then the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation, and the washed white precipitate was obtained. Then it was placed in an oven at 60 °C for drying to prepare 1,4-diaminobutane cadmium chloride crystals.
[0130] Example 10
[0131] This example provides a method for preparing single crystal 1,4-diaminobutane cadmium chloride crystals (hydrothermal synthesis method), which specifically includes the following steps:
[0132] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrochloric acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0133] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixed solution;
[0134] (S3) Transfer the mixed solution prepared in step (S2) into the inner lining of a 50 mL reaction kettle, load the kettle (place it flat and tighten it), react in an oven at 150 °C for 10 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0135] After the reaction kettle is cooled and the pressure is relieved, slowly pour out the supernatant liquid therein and retain the white precipitate; Assist in transferring the white precipitate to a 50 mL large centrifuge tube with a disposable pipette, and use the pipette to suck ethyl acetate (30 mL) to centrifuge and wash the crystal sample; Centrifuge the white precipitate repeatedly 5 times, pour out the upper layer liquid after each centrifugation, retain the precipitate, and repeat the above operation to add ethyl acetate to continue washing until the solvent is transparent after centrifugation to obtain a washed white precipitate, and then place it in a drying oven at 60 °C to dry to prepare 1,4-diaminobutane cadmium chloride crystals.
[0136] Example 11
[0137] This example provides a method for preparing single crystal 1,4-diaminobutane cadmium bromide crystals (hydrothermal synthesis method), which specifically includes the following steps:
[0138] (S1) Dissolve 0.01 mol of CdCO3 in 30 mL of hydrobromic acid, and mix well by magnetic stirring to obtain a cadmium carbonate solution;
[0139] (S2) Add 0.005 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixed solution;
[0140] (S3) Transfer the mixed solution prepared in step (S2) into the inner lining of a 50 mL reaction kettle, load the kettle (place it flat and tighten it), react in an oven at 120 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0141] After the reaction kettle is cooled and the pressure is relieved, slowly pour out the supernatant liquid therein and retain the white precipitate; Assist in transferring the white precipitate to a 50 mL large centrifuge tube with a disposable pipette, and use the pipette to suck ethyl acetate (30 mL) to centrifuge and wash the crystal sample; Centrifuge the white precipitate repeatedly 5 times, pour out the upper layer liquid after each centrifugation, retain the precipitate, and repeat the above operation to add ethyl acetate to continue washing until the solvent is transparent after centrifugation to obtain a washed white precipitate, and then place it in a drying oven at 60 °C to dry to prepare 1,4-diaminobutane cadmium bromide crystals.
[0142] Example 12
[0143] This embodiment provides a method for preparing a single-crystal 1,4-diaminobutane cadmium bromide crystal (hydrothermal synthesis method), which specifically includes the following steps:
[0144] (S1) Dissolve 0.01 mol of CdCO3 in 28 mL of hydrobromic acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0145] (S2) Add 0.015 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixed solution;
[0146] (S3) Load the mixed solution prepared in step (S2) into a 50 mL reaction kettle liner, install the kettle (place it flat and tighten it), react in an oven at 120 °C for 12 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0147] After the reaction kettle is cooled and the pressure is relieved, slowly pour out the supernatant liquid therein and retain the white precipitate; use a disposable pipette to assist in transferring the white precipitate to a 50 mL large centrifuge tube, and use a pipette to suck ethyl acetate (30 mL) to centrifuge and wash the crystal sample; centrifuge the white precipitate 5 times repeatedly, pour out the upper layer liquid after each centrifugation and retain the precipitate, then repeat the above operation to add ethyl acetate to continue washing until the solvent is transparent after centrifugation to obtain a washed white precipitate, and then place it in a drying oven at 60 °C to dry to prepare a 1,4-diaminobutane cadmium bromide crystal.
[0148] Example 13
[0149] This embodiment provides a method for preparing a single-crystal 1,4-diaminobutane cadmium bromide crystal (hydrothermal synthesis method), which specifically includes the following steps:
[0150] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrobromic acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0151] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixed solution;
[0152] (S3) Load the mixed solution prepared in step (S2) into a 50 mL reaction kettle liner, install the kettle (place it flat and tighten it), react in an oven at 180 °C for 10 h, then cool the reaction kettle to room temperature and relieve the pressure;
[0153] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was sucked with a pipette to centrifuge and wash the crystal sample. The white precipitate was centrifuged repeatedly 5 times. After each centrifugation, the upper layer liquid was poured out, and the precipitate was retained. Then, the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation, and the washed white precipitate was obtained. Then, it was placed in an oven at 60 °C for drying to prepare 1,4-diaminobutane cadmium bromide crystals.
[0154] Example 14
[0155] This example provides a method for preparing single crystal 1,4-diaminobutane cadmium bromide crystals (hydrothermal synthesis method), which specifically includes the following steps:
[0156] (S1) Dissolve 0.01 mol of CdCO3 in 25 mL of hydrobromic acid, and mix well with magnetic stirring to obtain a cadmium carbonate solution;
[0157] (S2) Add 0.01 mol of 1,4-diaminobutane to the cadmium carbonate solution obtained in step (S1), and continue magnetic stirring until the solution becomes viscous (milky white) to obtain a mixture;
[0158] (S3) Put the mixture prepared in step (S2) into the inner lining of a 50 mL reactor, load the reactor (place it flat and tighten it), react in an oven at 140 °C for 14 h, then cool the reactor to room temperature and depressurize it;
[0159] After the reactor was cooled and depressurized, the supernatant was slowly poured out, and the white precipitate was retained. The white precipitate was transferred to a 50 mL large centrifuge tube with the assistance of a disposable pipette, and ethyl acetate (30 mL) was sucked with a pipette to centrifuge and wash the crystal sample. The white precipitate was centrifuged repeatedly 5 times. After each centrifugation, the upper layer liquid was poured out, and the precipitate was retained. Then, the above operation was repeated to add ethyl acetate for continuous washing until the solvent was transparent after centrifugation, and the washed white precipitate was obtained. Then, it was placed in an oven at 60 °C for drying to prepare 1,4-diaminobutane cadmium bromide crystals.
[0160] The above description of the embodiments is for the convenience of those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art within the scope of the present invention without departing from the scope of the present invention should be within the protection scope of the present invention.
Claims
1. A single-crystal 1,4-diaminobutane cadmium halide crystal, characterized in that, Its chemical formula is C4N2H 14 CdX4; X is one of Cl, Br or I; In the single crystal of 1,4-diaminobutane cadmium halide, the central Cd 2+ cation coordinates with four individual and two adjacent bridging X - anions to form a CdX6 octahedron. The CdX6 octahedron layers and (C4N2H 14 ) 2+ cation layers interleave infinitely to form a two-dimensional layered structure or a one-dimensional branched chain structure.
2. The single crystal cadmium halide 1,4-diaminobutane according to claim 1, characterized in that, When X is Cl, the unit cell parameters of the single crystal cadmium chloride 1,4-diaminobutane are α = 90°, β = 101.586(7)°, γ = 90°.
3. A single crystal 1,4-diaminobutane cadmium halide crystal according to claim 1, characterized in that, When X is Br, the unit cell parameters of the single crystal cadmium chloride 1,4-diaminobutane crystal are α = 90°, β = 94.813(10)°, γ = 90°.
4. A method for preparing a single crystal cadmium halide 1,4-diaminobutane as claimed in any one of claims 1 to 3, characterized in that, It includes the following steps: (S1) Dissolve cadmium carbonate in hydrogen halide to obtain a cadmium carbonate solution; (S2) Mix the cadmium carbonate solution prepared in step (S1) with 1,4-diaminobutane, carry out a hydrothermal reaction, and perform post-treatment to obtain single-crystal 1,4-diaminobutane cadmium halide crystals.
5. The preparation method of a single crystal 1,4-diaminobutane cadmium halide crystal according to claim 4, characterized in that, In step (S1), the hydrogen halide is selected from one of HF, HCl, HBr, HI or HAt.
6. The preparation method of a single crystal 1,4-diaminobutane cadmium halide crystal according to claim 4, characterized in that, In step (S1), the dosage ratio of cadmium carbonate to hydrogen halide is 0.01 mol: 25 - 30 mL.
7. The preparation method of a single crystal 1,4-diaminobutane cadmium halide crystal according to claim 4, characterized in that, In step (S2), the molar ratio of the cadmium carbonate solution to 1,4-diaminobutane is 1: 0.5 - 1.
5.
8. The preparation method of a single crystal cadmium halide 1,4-diaminobutane according to claim 4, characterized in that, In step (S2), during the hydrothermal reaction, the temperature is 120 - 180 °C and the time is 10 - 14 h.
9. The preparation method of a single crystal cadmium halide 1,4-diaminobutane according to claim 4, characterized in that, In step (S2), the post-treatment specifically is to collect the precipitate obtained from the reaction after the reaction ends, wash the precipitate and then dry it.
10. Application of the single-crystal 1,4-diaminobutane cadmium halide crystal according to any one of claims 1 - 3 in photodetectors, data storage, and the photovoltaic field.