Shape-controllable metal organic complex and preparation method thereof

Abstract

The application discloses a metal organic complex with controllable morphology and a preparation method thereof, and belongs to the technical field of metal organic complex preparation. The preparation method of the metal organic complex with controllable morphology comprises the following steps: dissolving cuprous oxide and 4-hydroxythiophenol in anhydrous ethanol to form a mixed solution A; circulating nitrogen into the mixed solution A and performing air extraction and inflation to obtain a mixed solution B; and performing a heating reaction on the mixed solution B under stirring to obtain a reaction liquid capable of controlling the morphology of the metal organic complex; wherein the morphology of the metal organic complex is controlled by controlling the heating reaction time; and the reaction liquid is sequentially filtered, washed and dried to obtain the metal organic complex, wherein the morphology of the metal organic complex is linear or flaky. According to the method, linear or flaky two completely different morphologies can be stably and controllably obtained by only adjusting the heating reaction time, and the flexibility and convenience of morphology control are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of organometallic complex preparation technology, specifically to an organometallic complex with controllable morphology and its preparation method. Background Technology

[0002] Organometallic complexes, due to their unique physicochemical properties, have shown broad application prospects in various fields such as catalysis, material separation, and drug delivery, and have become one of the research hotspots in materials chemistry. The solvothermal method, as a commonly used and mature method for preparing organometallic complexes, has, through long-term development, facilitated the development of a variety of organometallic complex materials with diverse structures.

[0003] The physicochemical properties of low-dimensional organometallic complexes are closely related to their crystal particle size, crystal structure, and microstructure. Organometallic complexes with specific morphologies can have their performance optimized for specific applications. Therefore, morphology control of organometallic complexes is of great significance for expanding their application boundaries and improving their application efficiency. Currently, some research has been conducted both domestically and internationally on the morphology preparation of organometallic complexes. Related techniques mostly involve selecting different preparation methods and adjusting the types or ratios of reaction reagents to attempt to obtain products with different morphologies.

[0004] However, in the existing technology, there is still insufficient research on the precise and controllable preparation of metal-organic complexes with different morphologies for the same reactant system. There is a lack of simple, efficient and stable technical solutions for controlling the morphology of products, which results in insufficient flexibility in the morphology control of metal-organic complexes. This makes it impossible to meet the differentiated requirements of different application scenarios for their morphology and corresponding properties, thus limiting the in-depth application of low-dimensional metal-organic complex materials in various fields.

[0005] Therefore, how to provide a flexible and convenient method for preparing organometallic complexes with controllable morphology has become a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0006] The purpose of this invention is to provide a morphology-controllable organometallic complex and its preparation method, so as to overcome the problems of poor morphology controllability and complex control methods in the prior art under the same reactant system.

[0007] The present invention solves the above-mentioned technical problems through the following technical solution: This invention provides a method for preparing morphology-controllable organometallic complexes, comprising the following steps: S1. Dissolve cuprous oxide and 4-hydroxythiophenol in anhydrous ethanol to form a mixed solution A; S2. Nitrogen gas is introduced into mixed solution A, and the gas is pumped and purged in a cycle to obtain mixed solution B; S3. The mixed solution B is heated under stirring to obtain a reaction solution in which the morphology of the organometallic complex can be controlled; wherein, the morphology of the organometallic complex is controlled by controlling the heating reaction time. S4. The reaction solution is filtered, washed and dried sequentially to obtain a metal-organic complex, which has a linear or plate-like morphology.

[0008] A further improvement of the present invention is that the molar ratio of cuprous oxide to 4-hydroxythiophenol is 1:(2-8).

[0009] A further improvement of the present invention is that the concentration of cuprous oxide is 0.08–0.10 mol / L.

[0010] A further improvement of this invention is that the nitrogen gas is introduced for 5 to 20 minutes.

[0011] A further improvement of the present invention is that the temperature of the heating reaction is 83-90°C.

[0012] A further improvement of the present invention is that when the heating reaction time is 18 to 25 min, the morphology of the organometallic complex is linear.

[0013] A further improvement of the present invention is that when the heating reaction time is 23 to 36 h, the morphology of the organometallic complex is plate-like.

[0014] A further improvement of the present invention is that the washing process specifically involves washing with ethanol, deionized water, and ethanol in sequence.

[0015] A further improvement of the present invention is that the drying temperature is 40-70°C and the drying time is 5-24 h.

[0016] The present invention also provides a morphology-controllable organometallic complex, which is prepared by the morphology-controllable organometallic complex preparation method described above.

[0017] Compared with the prior art, the positive and progressive effects of the present invention are as follows: The method for preparing morphology-controllable organometallic complexes provided by this invention, while keeping the reaction system of cuprous oxide and 4-hydroxythiophenol constant, can stably and controllably obtain two distinctly different morphologies, linear or plate-like, by adjusting only a single variable—the heating reaction time. This method is simple to operate, avoids complex reagent screening and process changes, and significantly improves the flexibility and convenience of morphology control, providing an efficient technical approach for the targeted design of material morphologies for different application scenarios. By simply adjusting the reaction time, two morphologies with significant structural differences can be obtained in the same reaction system, thereby achieving effective modulation of the physicochemical properties of the material without changing its chemical composition, and expanding the adaptability of the organometallic complex in different application scenarios. Attached Figure Description

[0018] The accompanying drawings are provided to further understand the invention and constitute a part of this invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0019] Figure 1 This is a schematic diagram of the preparation process of the organometallic complex prepared in Example 1.

[0020] Figure 2 The image shows a SEM image of the linear organometallic complex prepared in Example 1.

[0021] Figure 3 The image shows a SEM image of the sheet-like organometallic complex prepared in Example 4. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] In the description of this invention, it should be understood that the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0024] It should also be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0025] It should be understood that although terms such as first, second, third, etc., may be used in the embodiments of the present invention to describe the preset range, these preset ranges should not be limited to these terms. These terms are only used to distinguish the preset ranges from one another. For example, without departing from the scope of the embodiments of the present invention, the first preset range may also be referred to as the second preset range, and similarly, the second preset range may also be referred to as the first preset range.

[0026] The accompanying drawings illustrate various structural schematic diagrams according to embodiments disclosed in this invention. These drawings are not to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.

[0027] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. This is an explanation of the present invention and not a limitation thereof.

[0028] This invention provides a method for preparing morphology-controllable organometallic complexes, comprising the following steps: S1. Dissolve cuprous oxide and 4-hydroxythiophenol in anhydrous ethanol to form a mixed solution A; S2. Nitrogen gas is introduced into mixed solution A, and the gas is pumped and purged in a cycle to obtain mixed solution B; S3. The mixed solution B is heated under stirring to obtain a reaction solution in which the morphology of the organometallic complex can be controlled; wherein, the morphology of the organometallic complex is controlled by controlling the heating reaction time. S4. The reaction solution is filtered, washed and dried sequentially to obtain a metal-organic complex, which has a linear or plate-like morphology.

[0029] This invention, by defining a specific reactant system (cuprous oxide and 4-hydroxythiophenol), using anhydrous ethanol as a solvent, and combining a nitrogen-protected vacuum and purging cycle, allows for the precise and controllable preparation of two different morphologies of organometallic complexes—linear and plate-like—by adjusting the simple parameter of heating reaction time. This fills the technological gap in easily controlling the morphology of a single reactant system and effectively overcomes the shortcomings of existing technologies, such as poor flexibility and insufficient stability in morphology control. Furthermore, the preparation method of this invention is simple, requiring only sequential mixing and dissolution, nitrogen protection, heating reaction, and post-treatment. It eliminates the need to change reagents, adjust proportions, or use complex equipment. Morphology control is achieved solely by adjusting the easily operable parameter of heating reaction time. The process exhibits good repeatability and high stability, significantly reducing the preparation cost and application threshold of organometallic complexes, making it suitable for large-scale preparation. It solves the problems of cumbersome control schemes and difficulty in widespread application of existing technologies. Using the preparation method of this invention, two specific morphologies of organometallic complexes—linear and plate-like—can be precisely prepared, and the products exhibit both morphologies... It can be specifically adapted to the performance requirements of different application scenarios—for example, linear products can optimize mass transfer efficiency in catalytic reactions, while sheet-like products can improve loading performance in substance separation or drug delivery, effectively breaking through the limitations of existing technologies on material application scenarios, broadening the application boundaries of organometallic complexes in multiple fields, and improving the application efficiency of materials; through nitrogen extraction and gas circulation treatment, impurity gases in the reaction system can be effectively removed, avoiding their interference with the reaction process and product morphology formation; at the same time, the heating reaction and morphology control parameters are clear, the process is highly controllable, and the consistency of product morphology and quality stability between batches can be guaranteed.

[0030] Specifically, the molar ratio of cuprous oxide to 4-hydroxythiophenol is 1:(2-8).

[0031] By limiting the molar ratio of cuprous oxide to 4-hydroxythiophenol to 1:(2-8), a suitable specific reactant system can be constructed, which can ensure sufficient coordination of reactants and stable reaction process, and avoid problems such as failure of morphology control or impurity of products due to imbalance of ratio.

[0032] Specifically, the concentration of cuprous oxide is 0.08–0.10 mol / L.

[0033] This parameter constraint ensures that the crystal nucleation and growth process is neither too violent (leading to amorphous or impurity phases) nor too slow (leading to incomplete reactions). It provides a stable, pure, and reproducible initial reaction environment for subsequent morphological evolution (from linear to plate-like) to be dominated by the single variable of "time". This range was obtained through extensive experimental optimization. Beyond this range, the regularity of morphological regulation will weaken and reproducibility will decrease.

[0034] Specifically, the nitrogen gas should be introduced for 5 to 20 minutes.

[0035] By setting the nitrogen purging time to 5–20 minutes, oxygen and water vapor in the reaction system (ethanol solvent and liquid surface space) can be thoroughly and efficiently eliminated. Its beneficial effects are: first, it completely eliminates oxygen interference and prevents cuprous oxide (Cu) oxidation. + It is oxidized to Cu² + First, it ensures that the reaction always proceeds within the designed chemical valence state and pathway. Second, it creates a strictly anhydrous and oxygen-free environment, avoiding the participation of water molecules in coordination or causing side reactions, thereby eliminating uncontrollable factors in morphology caused by environmental fluctuations, making the heating reaction time the dominant and only kinetic variable affecting the morphology.

[0036] Specifically, the temperature for the heating reaction is 83–90°C.

[0037] Temperatures above 83°C ensure that the ethanol solvent can effectively promote the dissolution, mass transfer, and reactivity of the reactants under certain self-generated pressure, which is a necessary energy condition for crystal growth. Controlling the upper limit at 90°C precisely limits the energy input level of the reaction system. Within this mild and precise temperature window, the reaction has sufficient driving force, but will not cause the reaction to be too fast, nucleation to explode, or produce thermal decomposition byproducts due to excessively high temperatures.

[0038] Specifically, when the heating reaction time is 18–25 min, the morphology of the organometallic complex is linear.

[0039] Specifically, when the heating reaction time is 23–36 h, the organometallic complex has a plate-like morphology.

[0040] Under fixed reactants, concentrations, atmospheres, and temperatures, reaction time directly controls the stage of crystal growth. A short reaction time of 18–25 minutes corresponds to the dominant directional growth stage along a one-dimensional direction (such as a specific crystal face), where the number of nuclei and the growth rate reach a balance, suppressing lateral growth and thus stably obtaining a linear morphology with a high aspect ratio. Extending the time to 23–36 hours, crystal growth enters a more thermodynamically stable stage, tending to reduce surface energy through Ostwald ripening or layered epitaxial growth, thus developing into a two-dimensional extended plate-like morphology. By simply and precisely setting the reaction time, two distinctly different products with uniform morphology can be obtained with high predictability within the same reaction system without changing any material composition. This completely solves the cumbersome and uncertain nature of existing technologies that require frequent changes of reagents or methods to try different morphologies, achieving true precision, convenience, and controllability.

[0041] Specifically, the washing process involves sequentially washing with ethanol, deionized water, and ethanol.

[0042] First ethanol wash: mainly removes a large number of organic byproducts adsorbed on the product surface and unreacted 4-hydroxythiophenol.

[0043] Deionized water washing: This is intended to wash away any residual inorganic salt ions or water-soluble impurities that may affect the performance of the material in subsequent applications (such as catalysis and sensing).

[0044] Secondary ethanol washing: Utilizing the volatility of ethanol, the moisture in the surface and pores of the product after water washing is replaced, which is beneficial for subsequent drying steps and prevents structural agglomeration or morphological damage caused by residual moisture during the drying process.

[0045] The washing process preserves the integrity of the target morphology to the greatest extent possible, while ensuring the high purity of the product, so that the final effect of morphology control can be truly reflected in the material.

[0046] Specifically, the drying temperature is 40–70℃, and the drying time is 5–24 hours.

[0047] Low temperature can effectively avoid the breakage, aggregation or curling of nanowires or nanosheets caused by capillary forces generated by rapid solvent evaporation, thus perfectly maintaining the morphological characteristics obtained after the reaction; the wide time range (5 to 24 h) provides operational flexibility, which can be adjusted according to the batch size and equipment conditions in actual production without damaging the final morphology and structure. The preparation method provided by this invention has a certain tolerance to process fluctuations, which is conducive to stable production.

[0048] Based on the same inventive concept, the present invention also provides a morphology-controllable organometallic complex, which is prepared by the morphology-controllable organometallic complex preparation method described above.

[0049] This invention employs an in-situ reaction method. Under nitrogen protection, cuprous oxide and 4-hydroxythiophenol react in anhydrous ethanol. By adjusting the reaction time, morphology-controllable metal complexes can be obtained, producing both linear and plate-like morphologies. The preparation method of this invention is simple, easy to operate, environmentally friendly, and operates under mild conditions. It does not require the addition of any surfactants, directing agents, templates, or other organic substances that could introduce impurities into the product. The product morphology exhibits high controllability and good reproducibility.

[0050] Example 1 See Figure 1 A method for preparing morphology-controllable organometallic complexes includes the following steps: 1. Add cuprous oxide (0.33 g) and 4-hydroxythiophenol (1.52 g) to anhydrous ethanol (25.00 mL) and stir for 10 min to obtain mixed solution A.

[0051] 2. Nitrogen gas is introduced into mixed solution A through a thin needle for 10 minutes, followed by three cycles of evacuation and refilling.

[0052] 3. Under stirring conditions, the mixture A prepared in step 2 above is heated to a reaction temperature of 85°C for a reaction time of 20 min.

[0053] 4. The reaction mixture was vacuum filtered, washed three times with ethanol, deionized water, and ethanol again, and then vacuum dried at 50°C for 10 h to obtain a linear organometallic complex with controllable morphology. See [link to relevant documentation]. Figure 2 .

[0054] Example 2 A method for preparing morphology-controllable organometallic complexes includes the following steps: 1. Add cuprous oxide (0.32 g) and 4-hydroxythiophenol (1.63 g) to anhydrous ethanol (26.00 mL) and stir for 10 min to obtain mixed solution A.

[0055] 2. Nitrogen gas is introduced into mixed solution A through a thin needle for 12 minutes, followed by evacuation and refilling three times.

[0056] 3. Under stirring conditions, the mixture A prepared in step 2 above is heated to a reaction temperature of 84℃ and a reaction time of 22 min.

[0057] 4. The mixture after reaction is filtered under vacuum, washed three times with ethanol, deionized water and ethanol, and dried under vacuum at 55°C for 12 h to obtain linear organometallic complexes with controllable morphology.

[0058] Example 3 A method for preparing morphology-controllable organometallic complexes includes the following steps: 1. Add cuprous oxide (0.30 g) and 4-hydroxythiophenol (1.56 g) to anhydrous ethanol (24.00 mL) and stir for 10 min to obtain mixed solution A.

[0059] 2. Nitrogen gas is introduced into mixed solution A through a thin needle for 8 minutes, followed by evacuation and refilling three times.

[0060] 3. Under stirring conditions, the mixture A prepared in step 2 above is heated to a reaction temperature of 86℃ and a reaction time of 18 min.

[0061] 4. The mixture after reaction is filtered under vacuum, washed three times with ethanol, deionized water and ethanol, and dried under vacuum at 60°C for 12 h to obtain linear organometallic complexes with controllable morphology.

[0062] Example 4 A method for preparing morphology-controllable organometallic complexes includes the following steps: 1. Add cuprous oxide (0.33 g) and 4-hydroxythiophenol (1.53 g) to anhydrous ethanol (25.00 mL) and stir for 10 min to obtain mixed solution A.

[0063] 2. Nitrogen gas is introduced into mixed solution A through a thin needle for 10 minutes, followed by three cycles of evacuation and refilling.

[0064] 3. Under stirring conditions, the mixture A prepared in step 2 above is heated to a reaction temperature of 85°C for a reaction time of 24 h.

[0065] 4. The reaction mixture was vacuum filtered, washed three times with ethanol, deionized water, and ethanol again, and then vacuum dried at 50°C for 10 h to obtain a morphology-controllable plate-like organometallic complex. (See [link to relevant documentation]). Figure 3 .

[0066] Example 5 A method for preparing morphology-controllable organometallic complexes includes the following steps: 1. Add cuprous oxide (0.36 g) and 4-hydroxythiophenol (1.62 g) to anhydrous ethanol (28.00 mL) and stir for 10 min to obtain mixed solution A.

[0067] 2. Nitrogen gas is introduced into mixed solution A through a thin needle for 10 minutes, followed by three cycles of evacuation and refilling.

[0068] 3. Under stirring conditions, the mixture A prepared in step 2 above is heated to a reaction temperature of 85°C for a reaction time of 28 h.

[0069] 4. The mixture after reaction is filtered under vacuum, washed three times with ethanol, deionized water and ethanol, and dried under vacuum at 50°C for 10 h to obtain a plate-shaped organometallic complex with controllable morphology.

[0070] Example 6 A method for preparing morphology-controllable organometallic complexes includes the following steps: 1. Add cuprous oxide (0.36 g) and 4-hydroxythiophenol (1.52 g) to anhydrous ethanol (30.00 mL) and stir for 10 min to obtain mixed solution A.

[0071] 2. Nitrogen gas is introduced into mixed solution A through a thin needle for 10 minutes, followed by three cycles of evacuation and refilling.

[0072] 3. Under stirring conditions, the mixture A prepared in step 2 above is heated to a reaction temperature of 86℃ for a reaction time of 30 h.

[0073] 4. The mixture after reaction is filtered under vacuum, washed three times with ethanol, deionized water and ethanol, and dried under vacuum at 60°C for 10 h to obtain a plate-like organometallic complex with controllable morphology.

[0074] The method for preparing morphology-controllable organometallic complexes provided by this invention is simple, easy to operate, environmentally friendly, and operates under mild conditions. The morphology of the product can be controlled by changing the reaction time. It does not require changing the reaction environment and conditions, nor does it require the addition of any surfactants, directing agents, templates, or other organic substances that would cause other impurities to be added to the product. The product morphology has high controllability and good reproducibility.

[0075] Finally, it should be noted that the embodiments listed above are merely one or more specific manifestations of the technical solution of this invention. Their purpose is to clearly illustrate the concept, principle, and application of this invention through specific examples, and is by no means intended to limit the scope of protection of this invention to these specific embodiments. In fact, the true value of this invention lies in its proposed technical ideas and innovations, rather than its manifestations or implementation methods.

[0076] For those skilled in the art, after thoroughly reading and understanding the technical solution of this invention, they are fully capable of making various changes, modifications, or equivalent substitutions to the specific implementation of the invention based on their own professional knowledge and skills. These changes may include, but are not limited to: adjusting the range of technical parameters, optimizing the algorithm flow to improve efficiency, and replacing some technical components to achieve better compatibility or reduce costs. As long as these modified technical solutions substantially retain the technical features claimed by the original invention, that is, they can still achieve the core functions and effects of this invention, then these changes should be considered to fall within the scope of protection of the pending claims of this invention.

[0077] Furthermore, with the continuous progress and development of technology, new technical means and methods are constantly emerging, which provides ample space for further improvement and perfection of this invention. Therefore, the scope of protection of this invention should also include reasonable and foresightful improvements and extensions based on existing technology. As long as these improvements and extensions do not depart from the basic principles and core concepts of this invention, they should be considered equivalents of this invention and are equally protected by patent rights.

Claims

1. A method for preparing morphology-controllable organometallic complexes, characterized in that, Includes the following steps: S1. Dissolve cuprous oxide and 4-hydroxythiophenol in anhydrous ethanol to form a mixed solution A; S2. Nitrogen gas is introduced into mixed solution A, and the gas is pumped and purged in a cycle to obtain mixed solution B; S3. The mixed solution B is heated under stirring to obtain a reaction solution in which the morphology of the organometallic complex can be controlled; wherein, the morphology of the organometallic complex is controlled by controlling the heating reaction time. S4. The reaction solution is filtered, washed and dried sequentially to obtain a metal-organic complex, which has a linear or plate-like morphology.

2. The method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, The molar ratio of cuprous oxide to 4-hydroxythiophenol is 1:(2-8).

3. The method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, The concentration of cuprous oxide is 0.08–0.10 mol / L.

4. The method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, Nitrogen gas is introduced over a period of 5 to 20 minutes.

5. The method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, The temperature for the heating reaction is 83–90℃.

6. The method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, When the heating reaction time is 18–25 min, the morphology of the organometallic complex is linear.

7. The method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, When the heating reaction time is 23–36 h, the organometallic complex has a plate-like morphology.

8. The method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, The washing process specifically involves sequentially washing with ethanol, deionized water, and then ethanol.

9. A method for preparing a morphology-controllable organometallic complex according to claim 1, characterized in that, The drying temperature is 40–70 °C, and the drying time is 5–24 h.

10. A morphology-controllable organometallic complex, characterized in that, It was prepared using the method for preparing morphology-controllable organometallic complexes as described in any one of claims 1 to 9.

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