A fluorescent gas sensing material, a preparation method thereof and application thereof in monitoring chlorinated volatile organic compounds
The synthesis of copper cluster-based metal-organic frameworks via a solvothermal method solves the problem of rapid and sensitive detection of trace amounts of chlorinated volatile organic compounds in existing technologies, enabling rapid detection of chlorinated volatile organic compounds.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
- Filing Date
- 2024-11-29
- Publication Date
- 2026-05-29
AI Technical Summary
Existing technologies are insufficient for rapid, sensitive, and real-time monitoring of trace amounts of chlorinated volatile organic compounds.
A copper cluster-based metal-organic framework material was synthesized using a solvothermal method to form a fluorescent gas sensing material with cyan fluorescence, which can be used to detect chlorinated volatile organic compounds.
Rapid and sensitive detection of CH2Cl2, CHCl3 and 1,2-DCE vapors was achieved, with a detection limit as low as 0.4 Pa (3.7 ppm), a response time of 10 s, a recovery time of 181 s, and the ability to respond stably multiple times.
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Abstract
Description
Technical Field
[0001] This application relates to a fluorescent gas sensing material, its preparation method, and its application in monitoring chlorinated volatile organic compounds, belonging to the field of gas sensor material technology. Background Technology
[0002] Gas sensors have gained increasing attention due to their wide applications in air quality monitoring, food safety monitoring, and early disease diagnosis. Fluorescent gas sensors, with their advantages of good sensitivity, selectivity, stability, and designability, represent a promising material detection technology. Among them, luminescent metal-organic frameworks (MOFs) are an emerging class of fluorescent materials with ultra-large surface area, adjustable pore size / shape, functionalized sites, and interesting luminescent properties, showing great potential for application in fluorescent gas sensors.
[0003] Chlorinated volatile organic compounds (VOCs) are widely used organic solvents and common intermediates. Due to their low boiling points and high vapor pressures, they readily evaporate into the air at room temperature, posing significant risks to the natural environment and human health. However, currently, there are few fluorescent sensors capable of real-time monitoring of trace amounts of gaseous chlorinated VOCs. Developing fluorescent gas sensors based on luminescent metal-organic framework materials is crucial for advancing chlorinated VOC monitoring technology. Summary of the Invention
[0004] To address the limitations of existing technologies for monitoring trace amounts of chlorinated volatile organic compounds (VOCs), this application proposes a fluorescent gas sensing technology that utilizes a copper cluster-based metal-organic framework material synthesized via a solvothermal method to achieve rapid and sensitive detection of trace VOCs.
[0005] The technical solution adopted in this application is as follows:
[0006] According to a first aspect of this application, a fluorescent gas sensing material is provided, including a copper cluster-based metal-organic framework material;
[0007] The chemical formula of the copper cluster-based metal-organic framework material is {[Cu3I3(TPSA)]·CH3CN} n ;
[0008] TPSA stands for N,N',N”-tris(3-pyridyl)thiophosphate triamide.
[0009] Optionally, the copper cluster-based metal-organic framework material belongs to the orthorhombic crystal system with space group Pca21.
[0010] Optionally, the crystallographic data of the copper cluster-based metal-organic framework material are as follows: α=β=γ=90°, Z=4.
[0011] Optionally, the structure of the copper cluster-based metal-organic framework material includes an asymmetric unit, which comprises a {Cu3I3S} cluster, a TPSA ligand, and an acetonitrile molecule.
[0012] The S in the {Cu3I3S} cluster originates from the S in TPSA.
[0013] Optionally, the {Cu3I3S} cluster consists of a μ3-I - Two μ2-I - One μ2-S and three tetracoordinate Cu + Composition, where the distance between Cu…Cu is in between.
[0014] Optionally, the TPSA ligand acts as a four-connected node connected to the four {Cu3I3S} clusters, and the {Cu3I3S} clusters also act as four-connected nodes connected to the four ligands.
[0015] Optionally, the {Cu3I3S} cluster is connected to the TPSA ligand to form a three-dimensional structure with a one-dimensional through-channel.
[0016] Acetonitrile molecules are located in the channel and form hydrogen bonds with the amino groups in the TPSA ligand.
[0017] According to another aspect of this application, a method for preparing the above-mentioned fluorescent gas sensing material is provided, comprising the following steps:
[0018] A mixture containing CuI, TPSA, and acetonitrile was heated to react and yield a copper cluster-based metal-organic framework.
[0019] The ratio of CuI, TPSA, and acetonitrile is based on the chemical formula {[Cu3I3(TPSA)]·CH3CN} n The element ratio meter in the middle.
[0020] Optionally, the conditions for the heating reaction include: a reaction temperature of 80–90°C and a reaction time of 48–96 h.
[0021] This application synthesizes a copper cluster-based metal-organic framework with cyan fluorescence via a solvothermal method.
[0022] According to another aspect of this application, the fluorescent gas sensing material obtained according to the above preparation method is used in monitoring chlorinated volatile organic compounds.
[0023] Optionally, the application is for monitoring trace amounts of chlorinated volatile organic compounds.
[0024] Optionally, the chlorinated volatile organic compound is selected from the vapor of at least one compound selected from CH2Cl2, CHCl3, and 1,2-DCE.
[0025] The beneficial effects of this application include:
[0026] The fluorescent gas sensing material provided in this application is a copper cluster-based metal-organic framework with cyan fluorescence synthesized by a solvothermal method. This fluorescent gas sensing material can be used for rapid and sensitive detection of CH2Cl2, CHCl3, and 1,2-DCE vapors. It is most sensitive and rapid for the detection of dichloromethane vapor, with a detection limit of 0.4 Pa (3.7 ppm) and a response time of 10 s. Attached Figure Description
[0027] Figure 1 This is a schematic diagram of the TPSA structure in an embodiment of this application;
[0028] Figure 2 This is a schematic diagram of the asymmetric unit of complex 1 in the test example of this application;
[0029] Figure 3 This is a schematic diagram of the structure of complex 1 in the test example of this application;
[0030] Figure 4 This is a schematic diagram showing the position of acetonitrile in the structure of complex 1 in the test example of this application;
[0031] Figure 5 The following are powder diffraction patterns in the test examples of this application, where (a) is the powder diffraction pattern of complex 1 after being immersed in water for different times; (b) is the powder diffraction pattern of complex 1 after being immersed in an aqueous solution with pH = 2-13 for 6 hours; and (c) is the powder diffraction pattern of complex 1 after being immersed in different organic solvents for 6 hours.
[0032] Figure 6 The thermogravimetric curve of complex 1 in the test example of this application;
[0033] Figure 7 The excitation and emission spectra of complex 1 in the test examples of this application;
[0034] Figure 8 This is a schematic diagram of the chlorinated hydrocarbon gas detection device in the test examples of this application;
[0035] Figure 9The following are the results of the detection of dichloromethane gas by complex 1 in the test examples of this application: (a) the in-situ fluorescence spectrum of complex 1 at different dichloromethane vapor pressures, (b) the linear relationship between the fluorescence intensity of complex 1 and the dichloromethane vapor pressure, (c) the response-recovery curve of complex 1 to dichloromethane vapor, (d) the response photographs of complex 1 to dichloromethane vapor at different times, (e) the response cycle of complex 1 to dichloromethane vapor, and (f) the persistent response of complex 1 to dichloromethane vapor.
[0036] Figure 10 The following are the results of the detection of 1,2-dichloroethane by complex 1 in the test examples of this application: (a) the in-situ fluorescence spectrum of complex 1 at different 1,2-dichloroethane vapor pressures, (b) the linear relationship between the fluorescence intensity of complex 1 and the 1,2-dichloroethane vapor pressure, (c) the response-recovery curve of complex 1 to 1,2-dichloroethane vapor, and (d) the response photographs of complex 1 to 1,2-dichloroethane vapor at different times.
[0037] Figure 11 The following are the results of the detection of chloroform by complex 1 in the test examples of this application: (a) is the in-situ fluorescence spectrum of complex 1 under different chloroform vapor pressures, (b) is the linear relationship between the fluorescence intensity of complex 1 and the chloroform vapor pressure, (c) is the response-recovery curve of complex 1 to chloroform vapor, and (d) is the response photograph of complex 1 to chloroform vapor at different times.
[0038] Figure 12 This is a summary of the monitoring of CH2Cl2, CHCl3 and 1,2-DCE gases. Detailed Implementation
[0039] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0040] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.
[0041] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.
[0042] Example 1: Synthesis of Fluorescent Gas Sensing Materials
[0043] CuI (0.1 mmol) and TPSA (0.03 mmol) were mixed in 6 mL of acetonitrile. After sonication, the mixture was heated at 85 °C for three days. After washing with acetonitrile, filtering, and drying, copper cluster-based metal-organic framework materials were obtained, with a yield of approximately 50.2% based on TPSA ligands.
[0044] The resulting copper cluster-based metal-organic framework material can be used as a fluorescent sensor and is labeled "complex 1".
[0045] The chemical formula of the copper cluster-based metal-organic framework material is {[Cu3I3(TPSA)]·CH3CN} n TPSA stands for N,N',N”-tris(3-pyridyl)thiophosphate triamide, and its structural formula is as follows: Figure 1 As shown.
[0046] Test Example 1 Structural Characterization
[0047] Crystal data analysis was performed on the copper cluster-based metal-organic framework material prepared in Example 1. The structure is shown in Table 1. It can be seen that complex 1 crystallizes in the orthorhombic space group Pca21, which is a non-centrosymmetric space group. The asymmetric unit of the complex contains a {Cu3I3S} cluster, a TPSA ligand, and an acetonitrile molecule. Figure 2 The {Cu3I3S} cluster consists of a μ3-I - Two μ2-I - One μ2-S and three tetracoordinate Cu + Composition, where the distance between Cu…Cu is in Between, less than the sum of van der Waals radii This indicates the presence of strong copper-copper interactions. The TPSA ligand is connected to four {Cu3I3S} clusters, acting as four-connected nodes, and the {Cu3I3S} clusters are connected to four ligands, also acting as four-connected nodes. The copper clusters and ligands connect to form a three-dimensional structure, the topology of which is shown below. Figure 3 As shown, the topology type is gsi, and the Schlafli symbol is {6}. 6 Viewed along the b-axis, the ligands and clusters of complex 1 connect to form a one-dimensional through-channel structure with a pore size of [missing information]. Acetonitrile molecules are located in the channel and form hydrogen bonds with the amino groups, with the H…N distance being… ( Figure 4 ).
[0048] The crystal data of complex 1 are shown in Table 1, and the main bond lengths and bond angles are shown in Table 2.
[0049] Table 1. Crystal structure data.
[0050]
[0051] Table 2. Main bond lengths and bond angles of the coordination compounds.
[0052]
[0053]
[0054] Stability Analysis of Test Example 2
[0055] After the powder of complex 1 was immersed in water for one week, the PXRD pattern remained consistent with the original pattern. Figure 5 a) indicates that the framework has good water stability. The compound also exhibits high resistance to acids and alkalis; its crystal structure remains unchanged after immersion in aqueous solutions with pH values of 2-13 for 6 hours. Figure 5 b). Solvent stability tests show that the complex remains stable in a variety of organic solvents, including cyclohexane, tetrahydrofuran, toluene, DMF, and CH3CH2OH. Figure 5 c). Thermogravimetric analysis showed that the structure of the complex could be stabilized to nearly 200℃ when the CH3CN molecule was lost. Figure 6 ).
[0056] Test Example 3 Fluorescence Performance
[0057] At room temperature, when the excitation wavelength is 377 nm, the solid-state fluorescence emission peak of complex 1 is at 485 nm, exhibiting cyan fluorescence. Figure 7 ).
[0058] Test Example 6: Detection of Chlorinated Hydrocarbon Gases by Complex 1
[0059] Through the in-situ gas detection device (see schematic diagram of the device) Figure 8 (As shown) is used to detect CH2Cl2, CHCl3 and 1,2-DCE gases.
[0060] Detection of dichloromethane gas by complex 1: The detection limit of complex 1 for dichloromethane vapor is 0.4 Pa (3.7 ppm), the response time is 10 s, the recovery time is 181 s, it can be cycled 10 times, and the response is stable for one month (e.g., Figure 9 (As shown).
[0061] Detection of Complex 1 against 1,2-dichloroethane: The limit of detection for the vapor of Complex 1 against 1,2-dichloroethane is 1.2 Pa (11.0 ppm), the response time is 296 s, and the recovery time is 81 s (as shown in Figure 10).
[0062] Detection of chloroform by complex 1: The limit of detection for chloroform vapor by complex 1 is 3.1 Pa (28.5 ppm), the response time is 10 s, and the recovery time is 17 s (e.g., ...). Figure 11 (As shown)
[0063] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A fluorescent gas sensing material, characterized in that, Including copper cluster-based metal-organic framework materials; The chemical formula of the copper cluster-based metal-organic framework material is {[Cu3I3(TPSA)]·CH3CN} n ; TPSA stands for N,N',N”-tris(3-pyridyl)thiophosphate triamide.
2. The fluorescent gas sensing material according to claim 1, characterized in that, The copper cluster-based metal-organic framework belongs to the orthorhombic crystal system with space group Pca21.
3. The fluorescent gas sensing material according to claim 1, characterized in that, The crystallographic data of the copper cluster-based metal-organic framework material are as follows: α=β=γ=90°, Z=4.
4. The fluorescent gas sensing material according to claim 3, characterized in that, The structure of the copper cluster-based metal-organic framework material includes an asymmetric unit, which comprises a {Cu3I3S} cluster, a TPSA ligand, and an acetonitrile molecule.
5. The fluorescent gas sensing material according to claim 4, characterized in that, The {Cu3I3S} cluster consists of a μ3-I - Two μ2-I - One μ2-S and three tetracoordinate Cu + Composition, where the distance between Cu…Cu is in between.
6. The fluorescent gas sensing material according to claim 4, characterized in that, The TPSA ligand acts as a four-connected node, connecting to four {Cu3I3S} clusters, and the {Cu3I3S} clusters also act as four-connected nodes, connecting to four ligands.
7. The fluorescent gas sensing material according to claim 6, characterized in that, The {Cu3I3S} cluster is connected to the TPSA ligand to form a three-dimensional structure with a one-dimensional through channel; Acetonitrile molecules are located in the channel and form hydrogen bonds with the amino groups in the TPSA ligand.
8. A method for preparing the fluorescent gas sensing material according to any one of claims 1 to 7, characterized in that, Includes the following steps: A mixture containing CuI, TPSA, and acetonitrile was heated to react and yield a copper cluster-based metal-organic framework.
9. The preparation method according to claim 8, characterized in that, The conditions for the heating reaction include: a reaction temperature of 80–90°C and a reaction time of 48–96 h.
10. The fluorescent gas sensing material according to any one of claims 1 to 7, or the fluorescent gas sensing material obtained by the preparation method according to claim 8 or 9, is used in monitoring chlorinated volatile organic compounds; Preferably, the application is for monitoring trace amounts of chlorinated volatile organic compounds; Preferably, the chlorinated volatile organic compound is selected from the vapor of at least one compound selected from CH2Cl2, CHCl3, and 1,2-DCE.