Preparation method of copper-cobalt-sulfur nanorod material
By using copper dibutyldithiocarbamate and cobalt dibutyldithiocarbamate as precursors, copper-cobalt sulfur nanorod materials are prepared under vacuum or inert atmosphere, which solves the problem of difficulty in synthesis of copper-cobalt sulfur nanorods in the prior art, and achieves uniform and controllable size distribution of nanorods and process controllability.
Patent Information
- Application Number
- CN202510415584.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-03
- Publication Date
- 2025-06-06
AI Technical Summary
It is difficult to effectively synthesize copper-cobalt sulfur nanorod materials in the prior art, and the synthesis methods are mostly concentrated on hydrothermal methods, and there is a lack of a controllable process route.
Copper-cobalt sulfur nanorod materials are prepared by heating up under vacuum or inert atmosphere by adjusting the reaction temperature to control the size distribution of nanorods by adjusting the reaction temperature.
The size distribution of copper-cobalt sulfur nanorods is achieved uniformly and controllable, with an average diameter of 7 to 10 nm and a length of 20 to 60 nm. The phase composition of the material is spinel phase, with good controllability in the process and suitable for mass production and industrialization.
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Figure CN120097392A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of nano material preparation, and in particular relates to a method for preparing a copper-cobalt-sulfur nanorod material with uniform and controllable size distribution. Background Art
[0002] In the field of nanomaterials, one-dimensional nanomaterials have unique dimensional characteristics and physical and chemical properties, and have broad application prospects in the fields of photodetectors, supercapacitors, sensors, etc. One-dimensional nanomaterials include nanorods, nanowires, nanotubes, nanobelts, etc. The physical and chemical properties of one-dimensional nanomaterials are closely related to their composition and structure. The controllable synthesis of one-dimensional nanomaterials has always been a hot topic in the field of nanomaterials science.
[0003] Copper Cobalt Sulfur (CuCo 2 S 4 ) is the spinel compound AB 2 X 4 Copper, cobalt and sulfur are typical representatives of the metal ions, with copper occupying the tetrahedral position and cobalt occupying the octahedral position. Copper, cobalt and sulfur are non-toxic, low-cost and have excellent physical and chemical properties. They have attracted extensive attention from scientists in the fields of photoelectric conversion devices, photocatalysis, energy storage and photothermal therapy. The performance of copper, cobalt and sulfur nanomaterials is affected by their morphology, structure and size. So far, copper, cobalt and sulfur materials can be synthesized by a variety of methods, including high-temperature solid-phase method, low-temperature solution method, hydrothermal method and so on. However, the synthesized copper, cobalt and sulfur nanomaterials are mostly in the form of zero-dimensional nanoparticles and two-dimensional nanosheets, and the synthesis methods are mostly concentrated on the hydrothermal method or the synthesis route based on the hydrothermal method. There are still few reports on the controllable synthesis of copper, cobalt and sulfur nanorods, so the process route for the controllable preparation of copper, cobalt and sulfur nanorods still needs to be developed. Summary of the invention
[0004] In order to solve the problem of difficulty in preparing copper-cobalt-sulfur nanorods, the present invention provides a method for preparing copper-cobalt-sulfur nanorod nanomaterials.
[0005] The preparation steps of a copper-cobalt-sulfur nanorod material are as follows: (1) Preparation of precursor dispersion Add 0.05-0.20 g of organic copper and 0.20-0.80 g of organic cobalt to 10-25 mL of the mixed solvent, stir evenly, and obtain a precursor dispersion; The organic copper is dibutyl copper dithiocarbamate; The organic cobalt is cobalt dibutyl dithiocarbamate; The mixed solvent is prepared by uniformly mixing dodecylamine and dodecanethiol at a volume ratio of 7:1 to 3:1, or by uniformly mixing oleylamine and dodecanethiol at a volume ratio of 7:1 to 3:1; (2) Preparation of copper-cobalt-sulfur nanorod materials In vacuum or inert atmosphere, the temperature is raised to 140-190°C and kept warm for 15-120 min; the mixture is washed with cyclohexane for 3 times, washed by ethanol centrifugation for 2 times, and dried to obtain copper-cobalt-sulfur nanorod material; The copper-cobalt-sulfur nanorod material is gray-black powder; the powder particles are in the shape of nanorods, the average diameter of the nanorods is 7-10 nm, and the length is 20-60 nm; the phase composition of the copper-cobalt-sulfur nanorods is spinel phase copper-cobalt-sulfur.
[0006] The further technical solution is as follows: In step (2), the vacuum condition is a vacuum pressure of 0.01 MPa.
[0007] In step (2), the inert atmosphere condition is nitrogen or argon.
[0008] The beneficial technical effects of the present invention are embodied in the following aspects: 1. In the process of preparing copper-cobalt-sulfur nanorods, the present invention uses copper dibutyl dithiocarbamate as a copper precursor and cobalt dibutyl dithiocarbamate as a cobalt precursor to prepare copper-cobalt-sulfur nanorods with uniform and controllable size. The average diameter of the nanorods is 7 to 10 nm and the length is 20 to 60 nm; the size distribution of the copper-cobalt-sulfur nanorods can be achieved by adjusting the reaction temperature.
[0009] The activity of copper dibutyl dithiocarbamate is better than that of cobalt dibutyl dithiocarbamate. It will preferentially decompose to form size-controlled nanoclusters. Then the nanoclusters have a certain catalytic activity, inducing the co-decomposition of copper dibutyl dithiocarbamate and cobalt dibutyl dithiocarbamate, and finally forming copper-cobalt-sulfur nanorods with uniform and controllable size.
[0010] 2. The preparation method of the present invention has low raw material cost, good process controllability, controllable product phase composition, uniform size distribution, and excellent quality, which is conducive to the mass production and industrialization of copper-cobalt-sulfur nanorods.
[0011] 3. The copper-cobalt-sulfur nanorod material prepared by the present invention can be used as an optical and electrical material in optoelectronic devices, can be used as a magnetic material in magnetic devices, and can also be used as an electrode material in energy conversion and storage devices; it provides a new material for constructing optoelectronic and electromagnetic devices and energy conversion and storage devices. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 This is the X-ray diffraction (XRD) pattern of the copper-cobalt-sulfur nanorods prepared in Example 1.
[0013] Figure 2 This is a transmission electron microscope (TEM) image of the manganese sulfide nanocones prepared in Example 1.
[0014] Figure 3This is the X-ray diffraction (XRD) pattern of the copper-cobalt-sulfur nanorods prepared in Example 2.
[0015] Figure 4 This is a transmission electron microscope (TEM) image of the copper-cobalt-sulfur nanorods prepared in Example 2.
[0016] Figure 5 This is an ultraviolet-visible spectrum (UV-Vis) diagram of the copper-cobalt-sulfur nanorods prepared in Example 2. DETAILED DESCRIPTION
[0017] The present invention will be further described below in conjunction with embodiments. Example 1
[0018] The preparation steps of a copper-cobalt-sulfur nanorod material are as follows: (1) Preparation of precursor dispersion In a round-bottom flask, 0.05 g of copper dibutyl dithiocarbamate and 0.20 g of cobalt dibutyl dithiocarbamate were added to a mixed solvent of 16 mL of dodecylamine and 4 mL of dodecanethiol, and the mixture was stirred evenly to obtain a precursor dispersion.
[0019] (2) Preparation of copper-cobalt-sulfur nanorod materials The round-bottom flask was evacuated, and the temperature was raised to 170°C under a vacuum pressure of 0.01 MPa and kept for 30 min. After the reaction was completed, the mixture was washed with cyclohexane 3 times, washed by ethanol centrifugation 2 times, and dried to obtain the copper-cobalt-sulfur nanorod material. The copper-cobalt-sulfur nanorod material obtained in Example 1 was a gray-black powder.
[0020] Depend on Figure 1 It can be seen that the characteristic diffraction peak in the XRD spectrum of the copper-cobalt-sulfur nanorods prepared in Example 1 corresponds to the copper-cobalt-sulfur of the spinel phase (PDF: 42-1450), indicating that the main composition of the material is copper-cobalt-sulfur (CuCo 2 S 4 ).
[0021] Depend on Figure 2 It can be seen that the copper-cobalt-sulfur powder particles prepared in Example 1 have a nanorod-like morphology and a uniform size distribution, with an average diameter of about 8.5 nm and an average length of about 29.0 nm. Example 2
[0022] The preparation steps of a copper-cobalt-sulfur nanorod material are as follows: (1) Preparation of copper-cobalt-sulfur nanorod materials In a round-bottom flask, 0.06 g of copper dibutyl dithiocarbamate and 0.24 g of cobalt dibutyl dithiocarbamate were added to a mixed solvent of 16 mL of oleylamine and 4 mL of dodecanethiol and stirred evenly to obtain a precursor dispersion.
[0023] (2) Preparation of copper-cobalt-sulfur nanorod materials The round-bottom flask with the precursor dispersion was filled with nitrogen for deoxygenation for 30 minutes, and the nitrogen atmosphere was maintained. The temperature was raised to 150°C and kept warm for 60 minutes. After the reaction, the mixture was washed with cyclohexane for 3 times, washed with ethanol by centrifugation for 2 times, and dried to obtain copper-cobalt-sulfur nanorod material.
[0024] Depend on Figure 3 It can be seen that the characteristic diffraction peak in the XRD spectrum of the copper-cobalt-sulfur nanorods prepared in Example 2 corresponds to the copper-cobalt-sulfur of the spinel phase (PDF: 42-1450), indicating that the main composition of the material is copper-cobalt-sulfur (CuCo 2 S 4 ).
[0025] Depend on Figure 4 It can be seen that the size distribution of the copper-cobalt-sulfur nanorods prepared in Example 2 is uniform, with an average diameter of about 7.7 nm and an average length of about 26.2 nm. The diameter and length are shorter than those in Example 1, indicating that the size of the copper-cobalt-sulfur nanorods can be controlled by controlling the reaction temperature under the condition that the ratio of copper dibutyldithiocarbamate to cobalt dibutyldithiocarbamate remains unchanged.
[0026] Depend on Figure 5 It can be seen that the copper-cobalt-sulfur nanorod material prepared in Example 2 has a wide absorption in the visible light and near-infrared region in the UV-Vis spectrum.
Claims
1. A method for preparing a copper-cobalt-sulfur nanorod material, characterized in that: The steps are as follows: (1) Preparation of precursor dispersion Add 0.05-0.20 g of organic copper and 0.20-0.80 g of organic cobalt to 10-25 mL of the mixed solvent, stir evenly, and obtain a precursor dispersion; The organic copper is dibutyl copper dithiocarbamate; The organic cobalt is cobalt dibutyl dithiocarbamate; The mixed solvent is prepared by uniformly mixing dodecylamine and dodecanethiol at a volume ratio of 7:1 to 3:1, or by uniformly mixing oleylamine and dodecanethiol at a volume ratio of 7:1 to 3:1; (2) Preparation of copper-cobalt-sulfur nanorod materials In vacuum or inert atmosphere, the temperature is raised to 140-190°C and kept warm for 15-120 min; the mixture is washed with cyclohexane for 3 times, washed by ethanol centrifugation for 2 times, and dried to obtain copper-cobalt-sulfur nanorod material; The copper-cobalt-sulfur nanorod material is gray-black powder; the powder particles are in the shape of nanorods, the average diameter of the nanorods is 7-10 nm, and the length is 20-60 nm; the phase composition of the copper-cobalt-sulfur nanorods is spinel phase copper-cobalt-sulfur.
2. The method for preparing a copper-cobalt-sulfur nanorod material according to claim 1, characterized in that: In step (2), the vacuum condition is a vacuum pressure of 0.01 MPa.
3. The method for preparing a copper-cobalt-sulfur nanorod material according to claim 1, characterized in that: In step (2), the inert atmosphere condition is nitrogen or argon.