Carboxyl small molecule compound modified MPM material, preparation method and application
By modifying MPM materials through amidation reaction and optimizing charge transport using metal-carboxylic acid coordination bonds and hydrogen bond networks, the problem of rapid recombination of photogenerated electrons and holes in MPM materials was solved, thereby improving photocatalytic efficiency and enabling its application in photocatalytic degradation of organic pollutants and marine antifouling.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA SHIPBUILDING INDUSTRY CORPORATION NO725 RESEARCH INSTITUTE
- Filing Date
- 2026-01-28
- Publication Date
- 2026-05-05
AI Technical Summary
Existing MPM materials suffer from rapid photogenerated electron-hole recombination, leading to low quantum efficiency and consequently poor photocatalytic performance.
Amide reactions are carried out between amino-containing MPM materials and carboxyl small molecule compounds to form carboxyl small molecule modified MPM materials. The synergistic effect of metal-carboxylic acid coordination bonds and hydrogen bonds is used to enhance framework connectivity and structural order, optimize charge transport paths, and suppress the recombination of photogenerated electron-hole pairs.
It significantly improves photoluminescence efficiency and photocatalytic performance, thereby enhancing photocatalytic performance and making it suitable for photocatalytic degradation of organic pollutants and marine antifouling.
Smart Images
Figure CN121972227A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalytic materials technology, and more specifically, to a carboxyl small molecule compound modified MPM material, its preparation method, and its application. Background Technology
[0002] Photocatalysis, which utilizes solar energy to drive chemical reactions, holds great promise for environmental remediation (such as the degradation of organic pollutants and marine antifouling) and energy sustainability. This technology relies on photocatalysts absorbing photons to generate electron-hole pairs, which in turn drive redox reactions, mineralizing recalcitrant pollutants (such as dyes and antibiotics) into harmless substances. However, the widespread application of photocatalysis is limited by issues such as the rapid recombination of photogenerated carriers, a narrow absorption range (mainly limited to the ultraviolet region), and poor catalyst stability and recyclability.
[0003] Molecular porous materials (MPMs) are a class of solid-state materials assembled from discrete molecules through weak interactions (such as hydrogen bonds). These materials were initially developed by Zaworotko's team (J. Am. Chem. Soc. 2013, 135, 10950-10953), with representative materials including MPM-1-TIFSIX[Cu2(ade)4(TiF6)2] and MPM-1-Cl([Cu2(ade)4Cl2]Cl2). Structurally, MPMs are primarily constructed through non-covalent interactions, potentially forming both intramolecular channels and intermolecular pores. Representative materials MPM-1-TIFSIX and MPM-1-Cl possess well-defined porous structures, promoting light capture and reactant diffusion. However, they still suffer from low charge separation efficiency; for example, MPM-1-TIFSIX and MPM-1-Cl exhibit rapid photogenerated electron-hole recombination, leading to low quantum efficiency and consequently poor photocatalytic performance.
[0004] In summary, existing MPM materials exhibit rapid photogenerated electron-hole recombination, resulting in low quantum efficiency and consequently poor photocatalytic performance.
[0005] In view of this, the present invention is hereby proposed. Summary of the Invention
[0006] The purpose of this invention is to propose a carboxyl small molecule compound modified MPM material, its preparation method and application, in order to solve the problem that the existing MPM materials exhibit rapid photogenerated electron-hole recombination, resulting in low quantum efficiency and thus poor photocatalytic effect.
[0007] To achieve the above objectives, the technical solution of the present invention is implemented as follows:
[0008] A method for preparing a carboxyl small molecule compound modified MPM material, wherein the preparation method involves an amidation reaction between an amino-containing MPM material and a carboxyl small molecule compound to form a carboxyl small molecule compound modified MPM material.
[0009] Furthermore, the preparation method includes the following steps:
[0010] S1. Adenine, copper nitrate trihydrate and anion source compound are stirred and reacted in a mixed solvent to obtain the MPM material mother liquor;
[0011] S2. Add the carboxyl small molecule compound powder to the MPM material mother liquor, stir to dissolve and react, and obtain the carboxyl small molecule compound modified MPM material mother liquor;
[0012] S3. The mother liquor of the MPM material modified by the carboxyl small molecule compound is centrifuged and dried to obtain the MPM material modified by the carboxyl small molecule compound.
[0013] Furthermore, the concentration of adenine in the mother liquor of the MPM material is 2.0~3.0 g / L, the concentration of copper nitrate trihydrate in the mother liquor of the MPM material is 1.5~2.0 g / L, the concentration of the anion source compound in the mother liquor of the MPM material is 1.5~2.0 g / L, and the concentration of the carboxyl small molecule compound in the mother liquor of the MPM material is 1.0~1.5 g / L.
[0014] Furthermore, the carboxyl small molecule compound is at least one of pyromellitic acid, oxalic acid, maleic acid, and phthalic acid.
[0015] Furthermore, the anion source compound is one of copper chloride and ammonium fluorotitanate.
[0016] Furthermore, the mixed solvent is at least two of water, ethanol, N,N-dimethylformamide, and acetonitrile.
[0017] Furthermore, in step S1, the reaction temperature is 20~80℃ and the reaction time is 2~24h; in step S2, the reaction temperature is 20~80℃ and the reaction time is 2~24h.
[0018] In step S3, the drying temperature is 40~150℃ and the drying time is 1~10h.
[0019] In a second aspect, the present invention provides a carboxyl small molecule compound modified MPM material, wherein the carboxyl small molecule compound modified MPM material is prepared using any one of the methods described above.
[0020] A third aspect of the present invention provides an application of the carboxyl small molecule compound modified MPM material described above in the field of photocatalysis.
[0021] Compared with the prior art, the carboxyl small molecule compound modified MPM material, its preparation method, and its application described in this invention have the following beneficial effects:
[0022] 1) The present invention discloses a carboxyl small molecule compound modified MPM material, its preparation method, and its application. An amino-containing MPM material undergoes an amidation reaction with a carboxyl small molecule compound to form a bridged connection, resulting in a modified MPM material with enhanced photocatalytic performance. The carboxyl small molecule compound acts as a molecular glue, combining with the metal-carboxylic acid coordination bonds and hydrogen bonds of the MPM material to enhance framework connectivity and structural order, achieving a "rigid-flexible balance." This not only enhances the chemical stability and structural order of the material through metal-carboxylic acid coordination but also optimizes the charge transport path through the supplementary hydrogen bond network, effectively promoting the rate of photogenerated charge separation and migration, and successfully suppressing the rapid recombination of photogenerated electron-hole pairs, thereby improving quantum efficiency and significantly enhancing photocatalytic performance.
[0023] 2) The carboxyl small molecule compound modified MPM material, its preparation method, and its application described in this invention are simple to operate, can be integrated in situ, and have good compatibility. The preparation method involves directly adding a carboxyl small molecule compound to the mother liquor after synthesizing the MPM material to initiate the reaction. This process requires no complex post-treatment or harsh conditions and can be completed using conventional solvents and at mild temperatures. The process is simple, efficient, and easily scalable.
[0024] 3) The carboxyl small molecule compound modified MPM material, preparation method and application described in this invention are applied to the field of photocatalysis, including photocatalytic degradation of organic pollutants, marine antifouling or antibacterial, directly promoting the application potential of MPM materials in pollutant degradation, marine antifouling and antibacterial fields, and ultimately laying a solid material foundation for the realization of efficient, stable and sustainable photocatalytic technology applications. Attached Figure Description
[0025] Figure 1 This is a schematic flowchart of a method for preparing a carboxyl small molecule compound modified MPM material according to an embodiment of the present invention;
[0026] Figure 2 The diagram shows the structures of MPM-1-TIFSIX (a) and MPM-1-TIFSIX (b) modified with pyromellitic acid prepared in Example 1 of this invention.
[0027] Figure 3Transmission electron microscopy (TEM) images of MPM-1-TIFSIX (a) and MPM-1-TIFSIX (b) modified with pyromellitic acid prepared in Example 1 of this invention;
[0028] Figure 4 The image shows the TEM morphology of the oxalic acid-modified MPM-1-TIFSIX prepared in Example 2 of this invention.
[0029] Figure 5 The images show the TEM morphology of MPM-1-Cl (a) and MPM-1-Cl (b) modified with terephthalic acid prepared in Example 3 of this invention.
[0030] Figure 6 This is a TEM image of the maleic acid-modified MPM-1-Cl prepared in Example 4 of the present invention. Detailed Implementation
[0031] To make the technical means and objectives and effects of the present invention easier to understand, the embodiments of the present invention will be described in detail below with reference to specific illustrations.
[0032] It should be noted that all directional and positional terms used in this invention, such as "up," "down," "left," "right," "front," "back," "vertical," "horizontal," "inner," "outer," "top," "lower," "lateral," "longitudinal," and "center," are only used to explain the relative positional relationships and connections between components in a specific state (as shown in the accompanying drawings). They are merely for the convenience of describing the invention and do not require the invention to be constructed and operated in a specific orientation; therefore, they should not be construed as limitations on the invention. Furthermore, descriptions involving "first," "second," etc., are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated.
[0033] In the description of this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal communication between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.
[0034] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0035] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.
[0036] The electronic structure of MPM materials limits the effective separation and migration of charges. Existing MPM materials exhibit rapid photogenerated electron-hole recombination, resulting in low quantum efficiency and consequently poor photocatalytic performance.
[0037] To address the aforementioned technical problems, the applicant proposes a method for preparing carboxyl small molecule compound-modified MPM materials in this invention. The preparation method involves an amidation reaction between an amino-containing MPM material and a carboxyl small molecule compound to form a carboxyl small molecule compound-modified MPM material.
[0038] The present invention discloses a method for preparing carboxyl small molecule compound-modified MPM materials. An amino-containing MPM material undergoes an amidation reaction with a carboxyl small molecule compound to form a bridged connection, resulting in a modified MPM material with enhanced photocatalytic performance. The carboxyl small molecule compound acts as a molecular glue, combining with the metal-carboxylic acid coordination bonds and hydrogen bonds of the MPM material to enhance framework connectivity and structural order, achieving a "rigid-flexible balance." This method enhances the chemical stability and structural order of the material through metal-carboxylic acid coordination, while optimizing charge transport paths through the supplementary hydrogen bond network. This effectively promotes the separation and migration of photogenerated charges, successfully suppressing the rapid recombination of photogenerated electron-hole pairs, thereby improving quantum efficiency and significantly enhancing photocatalytic performance.
[0039] Specifically, the preparation method includes the following steps:
[0040] S1. Adenine, copper nitrate trihydrate and anion source compound are stirred and reacted in a mixed solvent to obtain the MPM material mother liquor;
[0041] S2. Add the carboxyl small molecule compound powder to the MPM material mother liquor, stir to dissolve and react, and obtain the carboxyl small molecule compound modified MPM material mother liquor;
[0042] S3. The mother liquor of the MPM material modified by the carboxyl small molecule compound is centrifuged and dried to obtain the MPM material modified by the carboxyl small molecule compound.
[0043] In MPM materials, metallic copper forms coordination bonds with adenine, enhancing the material's chemical stability and structural order. Furthermore, the anions from the anion source compound in the MPM material form hydrogen bonds with the nitrogen atoms on adenine, optimizing the charge transport pathway through a hydrogen bond network.
[0044] This setup incorporates carboxyl-based small molecule compounds into the mother liquor after MPM material synthesis. Bridged connections are formed through the amidation reaction of the carboxyl groups with the amino groups on the MPM ligands, resulting in a modified MPM material with enhanced photocatalytic performance. The carboxyl-based small molecule compounds act as molecular "glue," strengthening framework connectivity and structural order. A "rigid-flexible balance" is achieved through the synergistic use of coordination bonds and hydrogen bonds: metal-carboxylic acid coordination enhances the chemical stability and structural order of the material, while the supplementary hydrogen bond network optimizes the charge transport path. This strategy successfully suppresses the rapid recombination of photogenerated electron-hole pairs, thereby improving quantum efficiency.
[0045] Specifically, the concentration of adenine in the mother liquor of the MPM material is 2.0~3.0 g / L, the concentration of copper nitrate trihydrate in the mother liquor of the MPM material is 1.5~2.0 g / L, the concentration of the anion source compound in the mother liquor of the MPM material is 1.5~2.0 g / L, and the concentration of the carboxyl small molecule compound in the mother liquor of the MPM material is 1.0~1.5 g / L.
[0046] A suitable concentration range can ensure that all raw materials participate fully in the reaction, while avoiding problems such as increased side reactions due to excessively high concentrations or incomplete reactions due to excessively low concentrations, thus ensuring the quality and performance of modified MPM materials.
[0047] Specifically, the carboxyl small molecule compound is at least one of pyromellitic acid, oxalic acid, maleic acid, and phthalic acid.
[0048] These compounds have suitable carboxyl structures, enabling them to undergo effective amidation reactions with amino-containing MPM materials to form stable bridging connections, while also providing a basis for the formation of hydrogen bond networks.
[0049] Specifically, the anion source compound is one of copper chloride and ammonium fluorotitanate.
[0050] This configuration facilitates the formation of hydrogen bond networks in MPM materials and optimizes the charge transport path.
[0051] Specifically, the mixed solvent is at least two of water, ethanol, N,N-dimethylformamide (DMF), and acetonitrile.
[0052] Combining multiple solvents can adjust the polarity, solubility, and other properties of the reaction system, providing a suitable environment for the reaction and facilitating its smooth progress and product formation.
[0053] Preferably, the volume of the mixed solvent is 75-100 mL.
[0054] Furthermore, in step S3, the drying temperature is 40~150℃, and the drying time is 1~10h.
[0055] Appropriate drying conditions can remove the solvent from the mother liquor, resulting in dried carboxyl small molecule compound modified MPM materials, while avoiding the problems of material structure damage or performance degradation caused by excessively high temperature or excessive time.
[0056] Preferably, in step S3, the drying temperature is 60~90℃ and the drying time is 2~7h.
[0057] Appropriate drying conditions can remove the solvent from the mother liquor, resulting in dried carboxyl small molecule compound modified MPM materials, while avoiding the problems of material structure damage or performance degradation caused by excessively high temperature or excessive time.
[0058] Specifically, in step S1, the reaction temperature is 20~80℃ and the reaction time is 2~24h.
[0059] Under these conditions, adenine, copper nitrate trihydrate, and anion source compounds can fully react to generate MPM material mother liquor, ensuring the full progress of the reaction while avoiding energy waste and possible side reactions caused by excessively high temperatures or prolonged reaction times.
[0060] Preferably, in step S1, the reaction temperature is 30~50℃ and the reaction time is 3~4h.
[0061] Under these conditions, adenine, copper nitrate trihydrate, and anion source compounds can fully react to generate MPM material mother liquor, ensuring the full progress of the reaction while avoiding energy waste and possible side reactions caused by excessively high temperatures or prolonged reaction times.
[0062] Specifically, in step S2, the reaction temperature is 20~80℃ and the reaction time is 2~24h.
[0063] The appropriate temperature and time enable the carboxyl small molecule compound to effectively undergo an amidation reaction with the components in the MPM material mother liquor, forming a carboxyl small molecule compound modified MPM material mother liquor, thus ensuring the smooth progress of the modification reaction.
[0064] Preferably, in step S2, the reaction temperature is 35~60℃ and the reaction time is 2~6h.
[0065] The appropriate temperature and time enable the carboxyl small molecule compound to effectively undergo an amidation reaction with the components in the MPM material mother liquor, forming a carboxyl small molecule compound modified MPM material mother liquor, thus ensuring the smooth progress of the modification reaction.
[0066] More specifically, the ratio of the sum of the masses of the adenine, copper nitrate trihydrate, and the anion source compound to the mass of the carboxyl small molecule compound is 1:0.10~1.
[0067] This ratio setting facilitates the full reaction of adenine, copper nitrate trihydrate, anion source compounds, and carboxyl small molecule compounds, making full use of raw materials, improving raw material utilization, and ensuring the generation of modified MPM materials with good photocatalytic performance.
[0068] Preferably, the ratio of the sum of the masses of adenine, copper nitrate trihydrate, and the anion source compound to the mass of the carboxyl small molecule compound is 1:0.20~0.25.
[0069] This ratio setting facilitates the full reaction of adenine, copper nitrate trihydrate, anion source compounds, and carboxyl small molecule compounds, making full use of raw materials, improving raw material utilization, and ensuring the generation of modified MPM materials with good photocatalytic performance.
[0070] More specifically, the volume of the mixed solvent is 60-120 mL.
[0071] Preferably, the volume of the mixed solvent is 72-100 mL.
[0072] In a second aspect, the present invention provides a carboxyl small molecule compound modified MPM material, wherein the carboxyl small molecule compound modified MPM material is prepared using any one of the methods described above.
[0073] In a third aspect, the present invention proposes an application of the carboxyl small molecule compound modified MPM material in the field of photocatalysis, including photocatalytic degradation of organic pollutants, marine antifouling or antibacterial applications.
[0074] Example 1
[0075] This embodiment proposes a method for preparing MPM materials modified with carboxyl small molecule compounds. The MPM material is MPM-1-TIFSIX, the carboxyl small molecule compound is trimesic acid, the anion source compound is ammonium fluorotitanate, and the mixed solvent is water and acetonitrile. The volume of the mixed solvent is 75 mL, and the mixed solvent includes 35 mL of acetonitrile and 40 mL of water.
[0076] The structural formulas of MPM-1-TIFSIX and pyromellitic acid-modified MPM-1-TIFSIX are shown below. Figure 2 The structural formula of MPM-1-TIFSIX is shown in [link to structural formula]. Figure 2 (a) The structural formula of MPM-1-TIFSIX modified with pyromellitic acid is shown in [reference needed]. Figure 2 (b).
[0077] Depend on Figure 2 It is known that the carboxyl group of pyromellitic acid undergoes an amidation reaction with the amino group of adenine, acting as a bridge to connect the MPM materials into an overall framework structure, while not affecting the original hydrogen bond network.
[0078] Specifically, such as Figure 1 As shown, the preparation method includes the following steps:
[0079] S1. Dissolve 0.1712g of adenine in a mixed solvent of 35mL acetonitrile and 40mL water by heating. After cooling, add 0.1482g of copper nitrate trihydrate and 0.1256g of ammonium fluorotitanate. Stir to dissolve and react. The reaction temperature is 30℃ and the reaction time is 4h to obtain the MPM-1-TIFSIX mother liquor.
[0080] S2. Add 0.0888g of pyromellitic acid to the MPM-1-TIFSIX mother liquor after the reaction in step one, stir to dissolve and react, the reaction temperature is 35℃ and the reaction time is 5h, to obtain the pyromellitic acid modified MPM-1-TIFSIX mother liquor.
[0081] S3. The mother liquor of MPM-1-TIFSIX modified with trimellitic acid is centrifuged and dried. The drying temperature is 60℃ and the drying time is 5h to obtain MPM-1-TIFSIX modified with trimellitic acid.
[0082] Specifically, the concentration of adenine in the mother liquor of the MPM material is 2.3 g / L, the concentration of copper nitrate trihydrate in the mother liquor of the MPM material is 2.0 g / L, the concentration of the anion source compound in the mother liquor of the MPM material is 1.7 g / L, and the concentration of the carboxyl small molecule compound in the mother liquor of the MPM material is 1.2 g / L.
[0083] Specifically, the ratio of the sum of the masses of adenine, copper nitrate trihydrate, and the anion source compound to the mass of the carboxyl small molecule compound is 1:0.20.
[0084] Example 2
[0085] In this embodiment, unlike in Example 1, the carboxyl small molecule compound is oxalic acid.
[0086] In step S2, the reaction temperature is 40°C and the reaction time is 2 hours.
[0087] In step S3, the drying temperature is 80°C and the drying time is 3 hours.
[0088] In step S2, the mass of oxalic acid is weighed as 0.1021g.
[0089] Specifically, the concentration of the carboxyl small molecule compound in the mother liquor of the MPM material is 1.4 g / L.
[0090] Specifically, the ratio of the sum of the masses of adenine, copper nitrate trihydrate, and the anion source compound to the mass of the carboxyl small molecule compound is 1:0.23.
[0091] Example 3
[0092] In this embodiment, unlike in Example 1, the material used is MPM-1-Cl, the carboxyl small molecule compound is maleic acid, the anion source compound is copper chloride, and the volume of the mixed solvent is 100 mL, which includes 50 mL of acetonitrile and 50 mL of water.
[0093] In step S1, the reaction temperature is 50°C and the reaction time is 3 hours.
[0094] In step S2, the reaction temperature is 40°C and the reaction time is 6 hours.
[0095] In step S3, the drying temperature is 50°C and the drying time is 7 hours.
[0096] In step S1, the mass of adenine is 0.2108g, the mass of copper nitrate trihydrate is 0.1641g, and the mass of copper chloride is 0.1825g.
[0097] In step S2, 0.1415 g of terephthalic acid is weighed.
[0098] Specifically, the concentration of adenine in the mother liquor of the MPM material is 2.1 g / L, the concentration of copper nitrate trihydrate in the mother liquor of the MPM material is 1.6 g / L, the concentration of the anion source compound in the mother liquor of the MPM material is 1.8 g / L, and the concentration of the carboxyl small molecule compound in the mother liquor of the MPM material is 1.4 g / L.
[0099] Specifically, the ratio of the sum of the masses of adenine, copper nitrate trihydrate, and the anion source compound to the mass of the carboxyl small molecule compound is 1:0.25.
[0100] Example 4
[0101] In this embodiment, unlike in Example 3, the carboxyl small molecule compound is maleic acid.
[0102] In step S2, the reaction temperature is 60°C and the reaction time is 2 hours.
[0103] In step S3, the drying temperature is 90°C and the drying time is 2 hours.
[0104] In step S2, the mass of maleic acid is weighed as 0.1354g.
[0105] Specifically, the ratio of the sum of the masses of adenine, copper nitrate trihydrate, and the anion source compound to the mass of the carboxyl small molecule compound is 1:0.24.
[0106] Performance testing
[0107] I. Morphological Test
[0108] TEM tests were performed on MPM-1-TIFSIX and the trimesolic acid-modified MPM-1-TIFSIX from Example 1. The test results are shown in [Figure 1]. Figure 3 TEM images of MPM-1-TIFSIX are shown below. Figure 3 (a) TEM image of MPM-1-TIFSIX modified with pyromellitic acid is shown in Figure 1. Figure 3 (b).
[0109] TEM tests were performed on the oxalic acid-modified MPM-1-TIFSIX in Example 2. The TEM morphology of the oxalic acid-modified MPM-1-TIFSIX is shown in the figure. Figure 4 .
[0110] TEM tests were performed on MPM-1-Cl and terephthalic acid-modified MPM-1-Cl in Example 3. The test results are shown in [Figure 1]. Figure 5 TEM morphology images of MPM-1-Cl are shown below. Figure 5(a) TEM image of terephthalic acid modified MPM-1-Cl is shown in Figure 1. Figure 5 (b).
[0111] TEM analysis was performed on the maleic acid-modified MPM-1-Cl in Example 4. The TEM morphology of the maleic acid-modified MPM-1-Cl is shown in the figure. Figure 6 .
[0112] Depend on Figure 3 and Figure 4 It can be seen that the overall morphology of MPM-1-TIFSIX modified with pyromellitic acid and MPM-1-TIFSIX modified with oxalic acid is not significantly different from that of MPM-1-TIFSIX.
[0113] Figure 5 and Figure 6 It can be seen that the terephthalic acid-modified MPM-1-Cl and maleic acid-modified MPM-1-Cl have similar overall morphology.
[0114] In summary, the carboxyl small molecule compound modified MPM material of the present invention has little difference in overall morphology compared with the unmodified material, and does not affect the original morphology.
[0115] II. Photocatalytic performance
[0116] The photocatalytic degradation experiments of methyl orange were carried out on MPM-1-TIFSIX modified with pyromellitic acid in Example 1, MPM-1-TIFSIX modified with oxalic acid in Example 2, MPM-1-Cl modified with terephthalic acid in Example 3, and MPM-1-Cl modified with maleic acid in Example 4. After 20 minutes of xenon lamp irradiation, the degradation rate of methyl orange was calculated, and the results are shown in Table 1.
[0117] Table 1. Degradation rate test of methyl orange
[0118]
[0119] As shown in Table 1, the methyl orange degradation rate of MPM-1-TIFSIX modified with pyromellitic acid in Example 1 was increased by 7.04% compared with MPM-1-TIFSIX; the methyl orange degradation rate of MPM-1-TIFSIX modified with oxalic acid in Example 2 was increased by 11.98% compared with MPM-1-TIFSIX; the methyl orange degradation rate of MPM-1-Cl modified with terephthalic acid in Example 3 was increased by 10.11% compared with MPM-1-Cl; and the methyl orange degradation rate of MPM-1-Cl modified with maleic acid in Example 4 was increased by 16.37% compared with MPM-1-Cl.
[0120] In summary, the carboxyl small molecule compound modified MPM material described in this invention can significantly improve photocatalytic performance.
[0121] While the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.
Claims
1. A method for preparing a carboxyl small molecule compound modified MPM material, characterized in that, The preparation method involves an amidation reaction between an amino-containing MPM material and a carboxyl small molecule compound to form a carboxyl small molecule compound-modified MPM material.
2. The method for preparing a carboxyl small molecule compound modified MPM material according to claim 1, characterized in that, The preparation method includes the following steps: S1. Adenine, copper nitrate trihydrate and anion source compound are stirred and reacted in a mixed solvent to obtain the MPM material mother liquor; S2. Add the carboxyl small molecule compound powder to the MPM material mother liquor, stir to dissolve and react, and obtain the carboxyl small molecule compound modified MPM material mother liquor; S3. The mother liquor of the MPM material modified by the carboxyl small molecule compound is centrifuged and dried to obtain the MPM material modified by the carboxyl small molecule compound.
3. The method for preparing a carboxyl small molecule compound modified MPM material according to claim 2, characterized in that, The concentration of adenine in the mother liquor of the MPM material is 2.0~3.0 g / L, the concentration of copper nitrate trihydrate in the mother liquor of the MPM material is 1.5~2.0 g / L, the concentration of the anion source compound in the mother liquor of the MPM material is 1.5~2.0 g / L, and the concentration of the carboxyl small molecule compound in the mother liquor of the MPM material is 1.0~1.5 g / L.
4. The method for preparing a carboxyl small molecule compound modified MPM material according to claim 2, characterized in that, The carboxyl small molecule compound is at least one of pyromellitic acid, oxalic acid, maleic acid, and phthalic acid.
5. The method for preparing a carboxyl small molecule compound modified MPM material according to claim 2, characterized in that, The anion source compound is one of copper chloride and ammonium fluorotitanate.
6. The method for preparing a carboxyl small molecule compound modified MPM material according to claim 2, characterized in that, The mixed solvent is at least two of water, ethanol, N,N-dimethylformamide, and acetonitrile.
7. The method for preparing a carboxyl small molecule compound modified MPM material according to claim 2, characterized in that, In step S1, the reaction temperature is 20~80℃ and the reaction time is 2~24h; in step S2, the reaction temperature is 20~80℃ and the reaction time is 2~24h.
8. The method for preparing a carboxyl small molecule compound modified MPM material according to claim 2, characterized in that, In step S3, the drying temperature is 40~150℃ and the drying time is 1~10h.
9. A carboxyl small molecule compound modified MPM material, characterized in that, The carboxyl small molecule compound modified MPM material is prepared using the method described in any one of claims 1 to 8.
10. The application of a carboxyl small molecule compound modified MPM material as described in claim 9 in the field of photocatalysis.