Method for realizing controllable synthesis of polyhedral cuprous oxide based on sound wave temperature control
By employing acoustic temperature control and a mixed ligand complex system, the synthesis challenges of pure-phase and polyhedral morphologies of cuprous oxide were solved, achieving simple, environmentally friendly, and efficient control, thus expanding the application prospects of the material.
Patent Information
- Application Number
- CN202610043068.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-14
- Publication Date
- 2026-05-15
AI Technical Summary
Existing technologies cannot simultaneously achieve efficient and precise control of the pure phase and polyhedral morphology of cuprous oxide. The synthesis process is complex, costly, and environmentally unfriendly, making it difficult to meet the requirements of green chemistry and industrial applications.
By employing acoustic temperature control technology combined with a mixed ligand complex system, the crystal growth rate of cuprous oxide can be controlled through ultrasonic cavitation effect and extreme temperature difference, thus achieving controllable synthesis of pure phase and polyhedral morphology.
This method enables the simple and controllable synthesis of cuprous oxide in both pure phase and polyhedral morphology, reducing costs, simplifying the process, meeting the requirements of green chemistry, and expanding the functional applications of the material.
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Figure CN122035926A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of new energy inorganic material preparation technology, specifically relating to a method for synthesizing pure phase cuprous oxide material, and particularly to a green preparation technology based on acoustic temperature control to achieve controllable synthesis of polyhedral cuprous oxide morphology. Background Technology
[0002] Cuprous oxide (Cu₂O), as an important p-type semiconductor material, has shown great application potential in fields such as photoelectrocatalysis, sensors, lithium-ion batteries, and solar energy conversion. The material's performance is highly dependent on its phase purity and microstructure. High-purity Cu₂O phases can avoid interference from impurities such as CuO or Cu on its intrinsic semiconductor properties; while specific polyhedral morphologies (such as cubes and octahedrons) can expose specific crystal faces, thereby significantly modulating its surface energy, active sites, and electronic structure, achieving targeted performance optimization.
[0003] However, achieving the controllable synthesis of pure cuprous oxide with specific morphologies in existing technologies still faces significant challenges, mainly in the following aspects: Firstly, controlling the purity of the phase is difficult: Cuprous oxide, as a metastable metal oxide, is easily oxidized to copper oxide (CuO) or reduced to elemental copper (Cu) during synthesis. To obtain pure Cu2O, traditional methods often require harsh conditions such as inert gas protection or the addition of complex reducing agents / complexing agents. These methods not only increase the complexity and cost of the process but may also introduce impurities, resulting in unsatisfactory product purity or poor reproducibility. High-temperature annealing is a common method for obtaining pure-phase materials, but the high-temperature process easily leads to abnormal grain growth or morphological destruction, making it difficult to achieve both "pure phase" and "morphology".
[0004] Secondly, the controllable synthesis of special morphologies faces high barriers: Although some methods for synthesizing cuprous oxide with different morphologies have been reported (such as hydrothermal, solvothermal, and template methods), these methods usually have obvious limitations or drawbacks. For example, template methods can effectively control morphology, but the introduction and removal of templates are cumbersome, costly, and prone to contaminating the product, making it difficult to meet the requirements of green chemistry and large-scale production. In hydrothermal or solvothermal methods, specific surfactants, structure-directing agents, or organic solvents are often required to regulate morphology. The use of these additives not only increases production costs but also brings difficulties in subsequent separation and purification and the risk of environmental pollution, which contradicts the current concept of green and sustainable chemical synthesis. More importantly, many existing methods have low tolerance for synthesis conditions and narrow parameter windows, making it difficult to achieve continuous and precise control of multiple polyhedral morphologies through a single, key variable, resulting in poor flexibility in morphology control. Moreover, under current technology, the polyhedral morphologies of cuprous oxide are highly homogeneous, mainly exhibiting a few regular polyhedra such as cubes and octahedrons, and the controllable synthesis of its diverse morphologies still faces significant challenges.
[0005] In summary, existing technologies, in pursuit of both "pure phase" and "special morphology," typically require the superposition of multiple stringent conditions, resulting in lengthy, complex, energy-intensive, and highly demanding synthetic routes. This complexity hinders the standardized preparation and industrial application of cuprous oxide functional materials. Therefore, there is an urgent need to develop a novel synthetic method that is simple, operates under mild conditions, is environmentally friendly, and can simultaneously achieve efficient and precise control over the phase purity and polyhedral morphology of cuprous oxide, while also expanding the cuprous oxide morphology library. Summary of the Invention
[0006] This invention provides a green method for the controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control. By utilizing the localized high temperature effect of ultrasonic cavitation and the extreme temperature differences under different temperature environments, the anisotropic growth rate of the crystal is controlled. Simultaneously, Cu is slowly released based on a mixed ligand complex system. 2+ Uniform nucleation enables green and controllable preparation of pure-phase cuprous oxide from hexagonal pyramidal to truncated octahedral morphology.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for the controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control, the method is as follows: (1) Preparation of mixed solvent: Take a certain amount of ethylene glycol and a certain amount of deionized water, mix them, stir for a certain time to form a fully miscible ethylene glycol aqueous solution; (2) Preparation of temperature control environment: Add equal amounts of constant 0℃ ice water mixture and constant room temperature water to the ultrasonic cleaner to create low temperature environment and room temperature environment respectively. Then place the ethylene glycol aqueous solution in step (1) in the low temperature environment and room temperature environment respectively for a certain period of time. (3) Preparation of mixed ligand complex precursor: Dissolve a certain amount of copper acetate monohydrate in the ethylene glycol aqueous solution in step (2), and sonicate for a certain time to obtain a mixed ligand complex solution; (4) Acoustic reaction: A certain amount of fructose is directly dissolved in the mixed ligand complex solution in step (3) and ultrasonically sonicated for a certain period of time; (5) Washing and drying of materials: After the reaction in step (4) is completed, a brick-red precipitate is formed. After washing and drying, hexagonal tetrapyramidal cuprous oxide and truncated octahedral cuprous oxide materials with different polyhedral morphologies are obtained, denoted as HT-Cu2O and TO-Cu2O respectively.
[0008] The above technical solution can achieve the following beneficial effects: The technical method described in this invention overcomes the limitations of high barriers, harsh conditions, and lengthy routes in the controllable synthesis of pure phase and special morphology of cuprous oxide. It utilizes a mixed ligand complex system to slowly release Cu. 2+ By achieving uniform nucleation, a novel approach was proposed to control the anisotropic growth rate of crystals through localized high temperatures caused by ultrasonic cavitation and extreme temperature differences under different temperature environments. This approach enables the ingenious regulation of the morphology of pure-phase cuprous oxide from hexagonal pyramids to truncated octahedrons, enriching the diversity of cuprous oxide materials in terms of morphology design and structural control, and expanding its functional application prospects.
[0009] The controllable morphologies of cuprous oxide polyhedra achieved by acoustic temperature control in this invention are hexagonal tetrahedral morphology and truncated octahedral morphology.
[0010] The method described in this invention features low raw material cost, simple equipment, and environmental friendliness. Its synthesis process is simple, easy to perform, and highly controllable. It slowly releases Cu through a dynamically balanced solution of a mixed ligand complex centered on copper ions and coordinated with acetate, ethylene glycol, and water molecules. 2+ By utilizing the local high temperature caused by ultrasonic cavitation and the extreme temperature differences under different temperature environments, it is possible to control the uniform nucleation and anisotropic growth of crystals, thereby achieving the morphological transformation of pure phase cuprous oxide from a hexagonal pyramid to a truncated octahedron.
[0011] The preparation method described in this invention can be used for the development of functional materials in clean energy fields such as photocatalysis, sensing, antibacterial, and new energy batteries. It is a novel material synthesis method that fits the innovation of green materials and environmental protection applications in multiple scenarios. Attached Figure Description
[0012] Figure 1 This is the X-ray powder diffraction pattern of the HT-Cu2O material prepared by the method in Example 1; Figure 2 This is a scanning electron microscope image of the HT-Cu2O material prepared by the method in Example 1.
[0013] Figure 3 This is the X-ray powder diffraction pattern of the TO-Cu2O material prepared by the method in Example 2; Figure 4 This is a scanning electron microscope image of the TO-Cu2O material prepared by the method in Example 2. Detailed Implementation
[0014] The following is in conjunction with the appendix Figure 1-4 The present invention will be further described as follows: By utilizing the extreme temperature differences between localized high temperatures caused by cavitation during ultrasonication and the growth environments at different temperatures, the anisotropic growth rate of crystals can be controlled, enabling the regulation of the polyhedral morphology of pure-phase cuprous oxide from hexagonal pyramids to truncated octahedrons. The expressions for these polyhedral morphologies are HT-Cu₂O and TO-Cu₂O, respectively, belonging to the field of new energy inorganic material preparation technology. Based on a dynamic equilibrium system of mixed ligand complexes centered on copper ions and coordinated with acetate, ethylene glycol, and water molecules, Cu is slowly released. 2+ This invention creatively proposes a method to control the anisotropic growth rate of crystals and induce significant morphological changes in pure-phase cuprous oxide by utilizing the localized high temperature caused by ultrasonic cavitation and extreme temperature differences under different temperature environments. The method described in this invention features low raw material costs, simple equipment, and environmental friendliness. Its synthesis process is simple, easy to perform, and highly controllable, ingeniously based on the slow release of Cu from a mixed ligand complex system. 2+ By utilizing the extreme temperature difference between the localized high temperature caused by ultrasonic cavitation and the external environment, the controllable evolution of the polyhedral morphology of pure-phase cuprous oxide was successfully achieved, expanding the diversity of this type of material in morphology design and structural control. This material has broad application prospects in the development of functional materials in the field of clean energy. Example
[0015] The preparation method of pure phase cuprous oxide morphology in a low-temperature environment is as follows: (1) Take 20 mL of ethylene glycol and 60 mL of deionized water and mix them. Stir for 10 min to form a well miscible ethylene glycol aqueous solution. (2) A constant 0°C ice-water mixture is added to the ultrasonic cleaner to create a low-temperature environment, and then the ethylene glycol aqueous solution in step (1) is placed in the low-temperature environment and left to stand for 30 min; (3) Dissolve 0.4 g of copper acetate monohydrate in the ethylene glycol aqueous solution in step (2) and sonicate for 2 min to obtain a mixed ligand complex solution; (4) Dissolve 0.8 g of fructose directly in the mixed ligand complex solution from step (3) and sonicate continuously for 120 min; (5) After the reaction in step (4) is completed, a brick-red precipitate is formed. After washing with water and drying (drying at 60°C in vacuum for 12 h), a cuprous oxide material with a hexagonal pyramidal morphology is obtained, denoted as HT-Cu2O.
[0016] Figure 1 The image shows the X-ray powder diffraction pattern of the HT-Cu2O material prepared by the method in Example 1. It can be observed that the HT-Cu2O material exhibits a well-matched cuprous oxide (Cu2O) crystal structure, and no other impurity phases were observed, which confirms the successful synthesis of pure-phase cuprous oxide in this invention.
[0017] Figure 2 The image shows a scanning electron microscope (SEM) image of the HT-Cu2O material prepared by the method in Example 1. It can be seen that the HT-Cu2O material exhibits a regular hexagonal pyramidal morphology, confirming the successful synthesis of the novel hexagonal pyramidal cuprous oxide. Example
[0018] The preparation method of room temperature truncated octahedral pure phase cuprous oxide morphology is as follows: (1) Take 20 mL of ethylene glycol and 60 mL of deionized water and mix them. Stir for 10 min to form a well miscible ethylene glycol aqueous solution. (2) Add constant room temperature water to the ultrasonic cleaner to create a room temperature environment, and then place the ethylene glycol aqueous solution in step (1) in the room temperature environment and let it stand for 30 min; (3) Dissolve 0.4 g of copper acetate monohydrate in the ethylene glycol aqueous solution in step (2) and sonicate for 2 min to obtain a mixed ligand complex solution; (4) Dissolve 0.8 g of fructose directly in the mixed ligand complex solution from step (3) and sonicate continuously for 120 min; (5) After the reaction in step (4) is completed, a brick-red precipitate is formed. After washing with water and drying (vacuum drying at 60°C for 12 h), a cuprous oxide material with a truncated octahedral morphology is obtained, which is denoted as TO-Cu2O.
[0019] Figure 3 The image shows the X-ray powder diffraction pattern of the TO-Cu2O material prepared by the method in Example 2. It can be seen that the change in the ambient temperature did not affect the crystal structure of the material. The TO-Cu2O material exhibits a well-matched cuprous oxide (Cu2O) crystal structure, and no other impurity phases were observed, which confirms the successful synthesis of pure-phase cuprous oxide in this invention.
[0020] Figure 4The image shows a scanning electron microscope (SEM) image of the TO-Cu2O material prepared by the method in Example 2. It can be seen that the TO-Cu2O material undergoes a significant morphological change with the change of the ambient temperature, exhibiting a novel truncated octahedral morphology with regular shape.
[0021] In summary, it can be seen that by changing the synthesis environment temperature based on the mixed ligand complex system, the pure phase cuprous oxide can be easily transformed from a hexagonal pyramidal morphology to a truncated octahedral morphology under the control of a low-temperature environment to a room-temperature environment.
[0022] The above descriptions are all preferred embodiments of the present invention. For those skilled in the art, any modifications to the present invention in various equivalent forms without departing from the principle of the present invention shall fall within the protection scope of the appended claims.
Claims
1. A method for controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control, characterized in that: The method is as follows: (1) Preparation of mixed solvent: Take a certain amount of ethylene glycol and a certain amount of deionized water, mix them, stir for a certain time to form a fully miscible ethylene glycol aqueous solution; (2) Preparation of temperature control environment: Add equal amounts of constant 0℃ ice water mixture and constant room temperature water to the ultrasonic cleaner to create low temperature environment and room temperature environment respectively. Then place the ethylene glycol aqueous solution in step (1) in the low temperature environment and room temperature environment respectively for a certain period of time. (3) Preparation of mixed ligand complex precursor: Dissolve a certain amount of copper acetate monohydrate in the ethylene glycol aqueous solution in step (2), and sonicate for a certain time to obtain a mixed ligand complex solution; (4) Acoustic reaction: A certain amount of fructose is directly dissolved in the mixed ligand complex solution in step (3) and ultrasonically sonicated for a certain period of time; (5) Washing and drying of materials: After the reaction in step (4) is completed, a brick-red precipitate is formed. After washing and drying, hexagonal tetrapyramidal cuprous oxide and truncated octahedral cuprous oxide materials with different polyhedral morphologies are obtained, denoted as HT-Cu2O and TO-Cu2O respectively.
2. The method for controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control according to claim 1, characterized in that: In step (1), the amount of ethylene glycol is 5-40 mL, the amount of deionized water is 40-80 mL, and the stirring time is 5-15 min.
3. The method for controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control according to claim 1, characterized in that: The settling time in step (2) is 10~50 min.
4. The method for controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control according to claim 1, characterized in that: In step (3), the amount of copper acetate monohydrate is 0.2~0.6 g, and the ultrasonic time is 1~3 min.
5. The method for controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control according to claim 1, characterized in that: In step (4), the fructose content is 0.4~1.2 g, and the ultrasonic time is 60~180 min.
6. The method for controllable synthesis of polyhedral cuprous oxide based on acoustic temperature control according to claim 1, characterized in that: The drying conditions in step (5) are 50~70℃ and 10~14 h of vacuum drying.