Benzene dithiol copper complex as well as preparation method and application thereof
By designing the structure of the benzediol copper complex Cu-m-BDT, the problem of ammonia detection being susceptible to water gas interference is solved, and high-sensitive ammonia detection in high humidity environments is achieved, which has industrial application value.
Patent Information
- Application Number
- CN202410025846.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-01-08
- Publication Date
- 2025-07-08
AI Technical Summary
The existing ammonia detection methods are susceptible to water gas interference, resulting in insufficient detection specificity and sensitivity.
Cu-m-BDT is used in the structure of Cu-m-BDT. Cu and three 1,3-benz-diethiol S atoms form a planar triangle, forming an infinitely continuous {CuS} chain, and is connected by a benzene ring. In the material, the hydrophobic benzene ring covers the chain CuS surface, effectively eliminating water and gas interference.
It improves the specificity and sensitivity of ammonia detection, and can accurately detect ammonia in high humidity environments, and is suitable for industrial production.
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Figure CN120271484A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of functional materials, and particularly relates to a copper benzenedithiol complex, a preparation method thereof, and an application thereof. Background Art
[0002] Ammonia detection is a common environmental monitoring method, which is commonly used in fields such as agriculture, animal husbandry, chemical industry, and environmental protection. Currently, the more common testing method is to utilize the principle of infrared spectroscopy and detect the ammonia concentration by measuring the absorption degree of the sample to infrared rays. However, the infrared vibration peak positions of ammonia and water are close, so the detection of ammonia is extremely susceptible to interference from water vapor. Summary of the Invention
[0003] To solve the above technical problems, the present invention first provides a copper benzenedithiol complex Cu-m-BDT, which is a complex formed by 1 molecule of Cu and 3 molecules of 1,3-benzenedithiol.
[0004] According to an embodiment of the present invention, the copper benzenedithiol complex Cu-m-BDT is a single crystal, belonging to the monoclinic system, and the space group of the crystal is P21 / n. The crystal parameters are: α = 90°, β = 107.89(3)°, γ = 90°, V = 747.7(3), Z = 8.
[0005] According to an embodiment of the present invention, the copper benzenedithiol complex Cu-m-BDT is formed by 1 Cu atom coordinating with the S atoms of 3 1,3-benzenedithiol molecules to form a planar triangle. In each planar triangle, the Cu atom is located at its center, and the 3 S atoms are respectively located at its vertices; every 4 planar triangles form a rhombus by sharing vertices pairwise and form an infinite continuous inorganic {CuS} chain along the b-axis direction, and the inorganic chains are connected by benzene rings.
[0006] The present invention also provides a preparation method of the copper benzenedithiol complex Cu-m-BDT as described above, including the following steps: ultrasonicating a copper source and 1,3-benzenedithiol in a solvent and then heating for reaction.
[0007] According to an embodiment of the present invention, the copper source is a copper halide, for example, copper iodide.
[0008] According to an embodiment of the present invention, the molar ratio of the copper source to 1,3-benzenedithiol is 1:(3 - 15), for example, 1:(8 - 12), such as 1:10.
[0009] According to an embodiment of the present invention, the temperature of the heating reaction is 70 - 100°C, and the reaction time is 6 - 96 h, for example, reacting at 80 - 90°C for 12 - 48 h.
[0010] According to an embodiment of the present invention, the solvent is a mixed solvent of alcohol and nitrile solvents, for example, a mixed solvent of ethanol and acetonitrile.
[0011] According to an embodiment of the present invention, when it is necessary to prepare a micron-sized copper benzenedithiol complex Cu-m-BDT, it can be prepared by the following method: Mix CuI with acetonitrile, and ultrasonically dissolve CuI at 0 - 30 °C under a power of 200 - 600 W, then sequentially add 1,3-benzenedithiol and 1 mL of ethanol, ultrasonically treat at 0 - 30 °C under a power of 200 - 600 W for 1 - 10 min, let stand for 0.5 - 12 h, filter by suction, and react the filtrate at 70 - 100 °C for 6 - 96 h.
[0012] According to an embodiment of the present invention, when it is necessary to prepare a nano-sized copper benzenedithiol complex Cu-m-BDT, it can be prepared by the following method: Mix CuI with 1,3-benzenedithiol, sequentially add acetonitrile and ethanol, then add HI, ultrasonically treat at 0 - 30 °C under a power of 400 W, and then react the system at 70 - 100 °C for 6 - 96 h.
[0013] The present invention also provides the application of the copper benzenedithiol complex Cu-m-BDT as described above in detecting alkaline gases.
[0014] According to an embodiment of the present invention, the alkaline gas is ammonia or volatile organic amine, such as triethylamine.
[0015] According to an embodiment of the present invention, the detection can be carried out at a humidity of 100% or less, such as 98% or less.
[0016] According to an embodiment of the present invention, the detection can be carried out in an environment of 0 - 120 °C.
[0017] According to an embodiment of the present invention, the concentration of the alkaline gas (such as ammonia or volatile organic amine) is 1 ppm or more, such as 10 ppm.
[0018] Beneficial effects
[0019] The present invention provides a copper benzenedithiol complex Cu-m-BDT, which is a complex formed by 1 molecule of Cu and 3 molecules of 1,3-benzenedithiol. In its structure, 1 Cu coordinates with the S atoms of 3 1,3-benzenedithiols to form a planar triangle. In each planar triangle, the Cu atom is located at its center, while the 3 S atoms are located at its vertices respectively; every 4 planar triangles form a rhombus by sharing vertices in pairs and form an infinite continuous inorganic {CuS} chain along the b-axis direction, and each inorganic chain is connected by benzene rings. From the composition and structure of the material, it can be seen that the hydrophobic benzene rings in the material cover the surface of the chain-like CuS. Therefore, the complex can effectively exclude the interference of water vapor during the detection of ammonia and volatile organic amines, improve the specificity and sensitivity of material testing, and has certain application value in industrial production. Description of the Drawings
[0020] Figure 1 It is the single crystal structure diagram of Cu-m-BDT.
[0021] Figure 2 It is the relationship diagram of the conductivity of Cu-m-BDT and temperature.
[0022] Figure 3 It is the relationship diagram of the natural logarithm value of the conductivity of Cu-m-BDT and the reciprocal of temperature.
[0023] Figure 4 It is the response data of Cu-m-BDT in different air humidity environments.
[0024] Figure 5 It is the response data of Cu-m-BDT to ammonia during normal temperature testing.
[0025] Figure 6 It is the response diagram of Cu-m-BDT when the test temperature is raised to 120 °C.
[0026] Figure 7 It is the response data of Cu-m-BDT to ammonia with different concentrations.
[0027] Figure 8 It is the response data of Cu-m-BDT to ammonia in different air humidity environments. Detailed Description of the Invention
[0028] The technical solutions of the present invention will be further described in detail below in combination with specific embodiments. It should be understood that the following embodiments are only used to illustrate and explain the present invention exemplarily, and should not be construed as limiting the protection scope 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.
[0029] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
[0030] Example 1
[0031] Synthesis of the complex Cu-m-BDT formed by CuI and 1,3-benzenedithiol via solvothermal method
[0032] Synthesis of larger crystals (micrometer-sized): CuI (0.050 mmol, 0.0095 g) was added to a 13 mL glass bottle, and then 8 mL of acetonitrile was added. It was ultrasonically treated at room temperature with a power of 400 W until CuI was completely dissolved. Then, 1,3-benzenedithiol (0.5 mmol, 57 μL) and 1 mL of ethanol were added in sequence. It was ultrasonically treated at room temperature with a power of 400 W for 10 min, allowed to stand for 1 h, filtered by suction, and the filtrate was placed in an oven at 85 °C for reaction for 2 d. After the reaction was completed, the solution was poured out and washed 3 times with acetonitrile and ethanol respectively to remove the unreacted ligands, and single crystals of Cu-m-BDT were obtained. The obtained material Cu-m-BDT is monoclinic. Its crystal parameters are: α = 90°, β = 107.89(3)°, γ = 90°, V = 747.7(3), Z = 8. The space group of the crystal is P21 / n, and the crystal structure diagram is as Figure 1 shown. As can be seen from Figure 1 Figure b in the middle, each Cu atom coordinates with the S atoms of 3 1,3-benzenedithiols to form a planar triangle. In each planar triangle, the Cu atom is located at its center, while the 3 S atoms are located at its vertices respectively; every 4 planar triangles form a rhombus in a vertex-sharing manner pairwise and form an infinite continuous inorganic {CuS} chain along the b-axis direction, and the inorganic chains are connected by benzene rings.
[0033] From the composition and structure of the material, it can be seen that the hydrophobic benzene rings in the material cover the surface of the chain-like CuS, so the material has hydrophobicity.
[0034] Example 2
[0035] Synthesis of the complex Cu-m-BDT formed by CuI and 1,3-benzenedithiol via solvothermal method
[0036] Synthesis of the test material (nanoscale): CuI (0.063 mmol, 0.012 g) and 1,3-benzenedithiol (0.63 mmol, 72 μL) were added into a 13 mL glass bottle. Then, 3 mL of acetonitrile and 5 mL of ethanol were added in sequence, followed by 10 μL of HI. After tightening the bottle cap, the mixture was ultrasonically treated at room temperature with a power of 400 W until all the solids were converted into a pale yellow flocculent intermediate product. After taking it out, it was transferred to an oven at 85 °C for a constant-temperature reaction for 1 day. After the reaction was completed, the solution was poured out and washed three times with acetonitrile and ethanol respectively to remove the unreacted ligands, and Cu-m-BDT single crystals were obtained.
[0037] Test Example 1: Temperature-dependent conductivity
[0038] The sample prepared in Example 2 was pressed into a powder tablet, and the conductivity was measured using a Keithley 4200 semiconductor test system. The temperature was changed and the corresponding conductivity k was calculated. The conductivity k was calculated according to the following formula:
[0039] k = L / RA
[0040] where k is the conductivity, L is the thickness of the material pressed into a thin sheet, R is the resistance, and A is the area of the thin sheet.
[0041] Figure 2 and 3 are the relationships between the conductivity of the material at different temperatures and its ln value and the reciprocal of the temperature. It can be seen from the figure that the conductivity of the material increases with the increase of temperature, indicating that the material has typical semiconductor behavior.
[0042] Test Example 2: Humidity sensitivity test
[0043] Assemble the humidity sensor testing system according to the method described in the literature LIN, YUAN, JIANG, HUIJIE, LIANG, GUANGLING, et al. The exceptionally high moisture responsiveness of a new conductive - coordination - polymer based chemiresistive sensor [J]. CrystEngComm, 2021, 23(19): 3549 - 3556 to test the humidity - sensing performance of the material prepared in Example 2. During the test, at a working voltage of 1V, different humidities are prepared by controlling the ratio of dry air to humid air. Place the prepared device (put the powder prepared in Example 2 into a quartz mortar, add an appropriate amount of ethanol, and gently grind it into a thick slurry with fine particles, and evenly drop - coat it on the Ag - Pd interdigital electrode to prepare the device) in the test chamber, introduce dry air, and then introduce the corresponding humid air after the baseline current is stable. After the response reaches saturation, introduce dry air again. The test results are as Figure 4 shown.
[0044] It can be Figure 4 seen that as the relative humidity continuously increases, the response value of the material also gradually increases, but the response value is still very small. When RH is less than 10%, there is almost no response. When RH = 98%, the response value is 16%. This shows that the material prepared by the present invention has good moisture resistance and can avoid the interference of water vapor during the process of testing ammonia concentration
[0045] Test Example 3 Gas - sensing performance test
[0046] The gas-sensing performance of the material prepared in Example 2 was tested by assembling a gas-sensing test system using the method described in YAO, MING-SHUI, TANG, WEN-XIANG, WANG, GUAN-E, et al. MOF Thin Film-Coated Metal Oxide Nanowire Array: Significantly Improved Chemiresistor Sensor Performance [J]. Advanced Materials, 2016, 28(26): 5229-5234. During the test, at a working voltage of 5 V, the prepared device (the powder prepared in Example 2 was placed in a quartz mortar, an appropriate amount of ethanol was added, and it was gently ground into a thick slurry with fine particles, and then evenly drop-coated on an Ag-Pd interdigital electrode to prepare the device) was placed in the test chamber, dry air was introduced, and after the baseline current was stable, NH3 with a concentration of 100 ppm was introduced. After the response reached saturation, dry air was introduced again. The test results are as Figure 5 shown.
[0047] It can be Figure 5 seen that this material has a strong response to ammonia during room-temperature testing, and the highest response value can reach 1020%. However, it cannot fully recover to the state before NH3 was introduced after stopping the introduction of NH3.
[0048] To shorten the recovery time of the device, the response and recovery performance of ammonia was tested at a temperature of 120 °C. At this temperature, the response value of the device to ammonia is 57%. The specific test results are as Figure 6 shown.
[0049] Test Example 4 Gas-Sensing Performance Test
[0050] By controlling the ratio of dry air and 100 ppm NH3, different concentrations of NH3 were prepared for detection. The test results are as Figure 7 shown. It can be Figure 7 seen that the material prepared in Example 2 has a response to 10 ppm ammonia, and its detection limit is as low as 1 ppm.
[0051] Test Example 5 Anti-Humidity Test for Ammonia
[0052] During the test, at a working voltage of 1 V, the device prepared as above was placed in the test chamber and dry air was introduced. By controlling the ratio of humid air, dry air and ammonia, different test conditions were prepared. After introducing the mixed gas, after the response reached saturation, dry air was introduced again. The test results are as Figure 8 shown. It can be Figure 8It can be seen that when there is humidity (i.e., RH > 0%), as the humidity increases, the response value of the material to ammonia does not change significantly, indicating that the influence of humidity on the ammonia detection of the material is small (when the humidity is 0%, the response is 142%; when the humidity is 90%, the response is 93%). That is to say, the material of the present application can avoid the interference of water vapor in the existing ammonia testing process and has high specificity for ammonia detection.
[0053] In summary, the material of the present invention has hydrophobicity, can effectively exclude the interference of water vapor in the testing process, detect ammonia with high sensitivity and specificity, and has certain application value in industrial production.
[0054] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A copper benzenedithiol complex Cu-m-BDT, characterized in that, It is a complex formed by 1 molecule of Cu and 3 molecules of 1,3-benzenedithiol.
2. The copper benzenedithiolate complex Cu-m-BDT according to claim 1, wherein The copper benzenedithiolate complex Cu-m-BDT is a single crystal, belonging to the monoclinic system. The space group of the crystal is P21 / n, and the crystal parameters are as follows: α = 90°, β = 107.89(3)°, γ = 90°, V = 747.7(3), Z = 8.
3. The copper benzenedithiolate complex Cu-m-BDT according to claim 1 or 2, characterized in that, The copper benzenedithiol complex Cu-m-BDT is formed by the coordination of 1 Cu atom with the S atoms of 3 1,3-benzenedithiol molecules to form a planar triangle. In each planar triangle, the Cu atom is located at its center, and the 3 S atoms are located at its vertices respectively; every 4 planar triangles form a rhombus by sharing vertices pairwise and form an infinite continuous inorganic {CuS} chain along the b-axis direction, and the inorganic chains are connected by benzene rings.
4. The preparation method of the copper benzenedithiolate complex Cu-m-BDT according to any one of claims 1-3, characterized in that, It includes the following steps: ultrasonically treating a copper source and 1,3-benzenedithiol in a solvent and then heating them for reaction.
5. The preparation method according to claim 4, characterized in that, The copper source is copper halide.
6. The preparation method according to claim 4 or 5, characterized in that The molar ratio of the copper source to 1,3-benzenedithiol is 1:(3 - 15).
7. The preparation method according to any one of claims 4-6, characterized in that The heating reaction is carried out at 70 - 100 °C for 6 - 96 h.
8. The preparation method according to any one of claims 4-7, characterized in that When it is necessary to prepare the micron-sized copper benzenedithiol complex Cu-m-BDT, the following method is used for preparation: mixing CuI and acetonitrile, ultrasonically treating at 200 - 600 W power at 0 - 30 °C until CuI dissolves, then sequentially adding 1,3-benzenedithiol and 1 mL of ethanol, ultrasonically treating at 200 - 600 W power at 0 - 30 °C for 1 - 10 min, standing for 0.5 - 12 h, filtering by suction, and reacting the filtrate at 70 - 100 °C for 6 - 96 h; Alternatively, when it is necessary to prepare the nano-sized copper benzenedithiol complex Cu-m-BDT, the following method is used for preparation: mixing CuI and 1,3-benzenedithiol, sequentially adding acetonitrile and ethanol, then adding HI, ultrasonically treating at 200 - 600 W power at 0 - 30 °C, and then reacting the system at 70 - 100 °C for 6 - 96 h.
9. Use of the copper benzenedithiol complex Cu-m-BDT according to any one of claims 1 - 3 in detecting alkaline gases.
10. The application according to claim 9, wherein The alkaline gas is ammonia or volatile organic amine; Preferably, the detection is carried out at a humidity below 100%; Preferably, the detection is carried out in an environment of 0 - 120 °C; Preferably, the concentration of the alkaline gas is 1 ppm or more.