阅读说明：本技术 一种竹叶状氧化铜纳米片及其制备方法 (Bamboo leaf-shaped copper oxide nanosheet and preparation method thereof ) 是由 刘晓伟 杨宝朔 商继涛 艾远 于 2021-10-20 设计创作，主要内容包括：本发明公开了一种竹叶状氧化铜纳米片及其制备方法。方法如下：步骤S1：将铜盐溶解到去离子水-乙醇的混合溶液中制成溶液A；将氢氧化钠和柠檬酸三钠溶解到去离子水中制成溶液B；步骤S2：将溶液A和溶液B混合,搅拌均匀后得到具有大量蓝色沉淀的悬浊液C；步骤S3：将悬浊液C在混合气体中80～120℃下加热,得到黑色沉淀产物,冷却至室温；步骤S4：依次采用去离子水和丙酮分别对的沉淀产物进行离心洗涤,每次洗完后离心并倒掉沉淀以上的滤液；步骤S5：烘干沉淀,得到竹叶状氧化铜纳米片。与现有的制备方法相比,产物具有特殊的竹叶状形态、分散性好,且可通过控制温度进一步控制粒径大小,同时具有流程简单,一步合成,易于操作,反应要求的条件低的特点。(The invention discloses a bamboo leaf-shaped copper oxide nanosheet and a preparation method thereof. The method comprises the following steps: step S1: dissolving a copper salt into a mixed solution of deionized water and ethanol to prepare a solution A; dissolving sodium hydroxide and trisodium citrate into deionized water to prepare solution B; step S2: mixing the solution A and the solution B, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates; step S3: heating the suspension C in mixed gas at 80-120 ℃ to obtain a black precipitate product, and cooling to room temperature; step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates; step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet. Compared with the existing preparation method, the product has special bamboo leaf-shaped form and good dispersibility, the particle size can be further controlled by controlling the temperature, and the preparation method has the characteristics of simple process, one-step synthesis, easy operation and low reaction requirement condition.)

1. A preparation method of bamboo leaf-shaped copper oxide nanosheets is characterized by comprising the following steps:

step S1: dissolving a copper salt into a mixed solution of deionized water and ethanol to prepare a solution A; dissolving sodium hydroxide and trisodium citrate into deionized water to prepare solution B;

step S2: mixing the solution A and the solution B, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates;

step S3: heating the suspension C in mixed gas at 80-120 ℃ to obtain a black precipitate product, and cooling to room temperature;

step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates;

step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet.

2. The method of claim 1, wherein: in the step S1, the copper salt is copper nitrate, copper chloride or copper sulfate, and the concentration is 0.1-1 mol/L.

3. The method of claim 1, wherein: in the step S1, the volume ratio of the deionized water to the ethanol in the mixed solution of the deionized water and the ethanol is 1-10: 1.

4. The method of claim 1, wherein: in the step S1, the concentration of sodium hydroxide in the solution B is 0.1-1 mol/L, and the molar ratio of sodium hydroxide to trisodium citrate is 10-50: 1.

5. The method of claim 1, wherein: in the step S2, the volume ratio of the solution A to the solution B is 1-5: 1.

6. The method of claim 1, wherein: in the step S2, the stirring condition is stirring for 1-5 min at 20-30 ℃, and the stirring speed is 100-500 rpm/min.

7. The method of claim 1, wherein: in the step S3, the volume fraction of air in the mixed gas is 60-80%, and the volume fraction of oxygen is 40-20%; in step S3, the heating time is 1-2 h.

8. The method of claim 1, wherein: in the step S4, the centrifugal washing frequency is 2-3 times, each time is 1-2 min, and the centrifugal speed is 4000-5000 rpm/min.

9. The method of claim 1, wherein: in the step S5, the drying environment is an air atmosphere, the drying temperature is 50-60 ℃, and the drying time is 1-5 h.

10. A bamboo leaf-shaped copper oxide nanosheet, characterized in that: prepared by the method of any one of claims 1-9; the length of the bamboo leaf-shaped copper oxide nano sheet is 300-1000 nm.

Technical Field

The invention belongs to the field of preparation methods of semiconductor nano materials, and particularly relates to a bamboo leaf-shaped copper oxide nanosheet and a preparation method thereof.

Background

Copper oxide is an important narrow-band gap p-type transition metal oxide, is rich in natural resources, low in price, non-toxic and simple to synthesize, has huge application potential in various applications such as gas sensors, supercapacitors, solar photovoltaics, lithium ion batteries, photocatalysis, super-hydrophobic surfaces, superconducting materials, biological medicines and the like due to excellent properties such as light, heat, electricity, catalysis and the like, and can be compounded with other materials to obtain more excellent performance.

The performance of the copper oxide with the nanometer scale is closely related to the shape, structure, size and surface appearance of the copper oxide, and the preparation of the copper oxide nanometer material with the controllable appearance is the basis of the development and application of the copper oxide nanometer material, and becomes a research hotspot at present. To date, there have been a large number of reports in the literature of various copper oxide nanostructures having different morphologies, such as nanowires, nanoneedles, nanorods, nanosheets, nanospheres, nanoflowers, nanorings, nanoplates, nanotubes, and pores, among others. The copper oxide nanosheet is a hotspot of a copper oxide nanomaterial due to better performances in the aspects of optics, catalysis, magnetism and the like, and further comprises various sheet structures, such as two-dimensional sheet structures, petal structures, leaf structures and the like. Among them, studies on bamboo-leaf-shaped nanosheets have been rare.

In addition, at present, many related copper oxide nano-material preparation methods mainly focus on a hydrothermal method, a thermal oxidation method and the like, and the methods have the defects of high temperature and high pressure, long reaction time, complex process and the like, so that the large-scale preparation of the copper oxide nano-material is greatly restricted, and the development and application of the bamboo leaf-shaped copper oxide nano-sheet are further restricted.

In conclusion, the development of the preparation method of the bamboo leaf-shaped copper oxide nanosheet, which can be realized by simple heating, has the advantages of simple process, low requirement on reaction conditions, good controllability (shape and size) and easy large-scale application, has important significance.

Disclosure of Invention

Aiming at the technical problems, the invention provides a bamboo leaf-shaped copper oxide nanosheet and a preparation method thereof. According to the invention, trisodium citrate is introduced as an auxiliary template, copper oxide nanosheets with good bamboo leaf morphology can be synthesized in one step through simple heating reaction and process optimization, and the morphology and size of the product can be further controlled by controlling the heating temperature; meanwhile, the method has the characteristics of simple flow, one-step synthesis, low requirement on conditions, low cost and easiness in large-scale production.

The scheme adopted by the invention for solving the technical problems is as follows:

a preparation method of bamboo leaf-shaped copper oxide nanosheets is characterized by comprising the following steps:

step S1: dissolving a copper salt into a mixed solution of deionized water and ethanol to prepare a solution A; dissolving sodium hydroxide and trisodium citrate into deionized water to prepare solution B;

step S2: mixing the solution A and the solution B, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates;

step S3: heating the suspension C in mixed gas at 80-120 ℃ to obtain a black precipitate product, and cooling to room temperature;

step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates;

step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet.

Further, the copper salt in the step S1 is copper nitrate, copper chloride or copper sulfate, and the concentration is 0.1-1 mol/L.

Further, in the step S1, the volume ratio of the deionized water to the ethanol in the deionized water-ethanol mixed solution is 1-10: 1. Preferably, the volume ratio of the deionized water to the ethanol in the deionized water-ethanol mixed solution is 1: 1.

Further, in the step S1, the concentration of sodium hydroxide in the solution B is 0.1-1 mol/L, and the molar ratio of sodium hydroxide to trisodium citrate is 10-50: 1.

Further, in the step S2, the volume ratio of the solution A to the solution B is 1-5: 1.

Further, in the step S2, the stirring condition is stirring for 1-5 min at 20-30 ℃, and the stirring speed is 100-500 rpm/min.

Further, in the step S3, the volume fraction of air in the mixed gas is 60 to 80%, and the volume fraction of oxygen is 40 to 20%.

Further, in the step S3, the bamboo leaf-shaped copper oxide sodium rice flakes with good dispersibility and a length of 300-500 nm are obtained by heating at 80-100 ℃ for 1-2 hours;

further, in the step S3, the bamboo leaf-shaped copper oxide sodium rice sheet with good dispersibility and 500-1000 nm is obtained by heating at 100-120 ℃ for 1-2 h.

Further, in the step S4, the centrifugal washing frequency is 2-3 times, each time is 1-2 min, and the centrifugal rotating speed is 4000-5000 rpm/min.

Further, in the step S5, the drying environment is an air atmosphere, the drying temperature is 50-60 ℃, and the drying time is 1-5 h.

In another aspect, the present invention provides a bamboo-leaf-shaped copper oxide nanosheet prepared by the above method, wherein the length of the bamboo-leaf-shaped copper oxide nanosheet is 300-1000 nm.

The invention also provides application of the bamboo leaf-shaped copper oxide nanosheet in the fields of photoelectric and photo-thermal materials.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

(1) the invention realizes the preparation of the bamboo leaf-shaped copper oxide nanosheet by introducing trisodium citrate as a template agent to carry out simple heating reaction and process optimization, and the product has good bamboo leaf shape and good dispersibility.

(2) The invention further realizes the controllable preparation of different particle sizes and shapes by controlling the heating temperature.

(3) The method has the advantages of simple flow, easy operation, low reaction requirement condition, no need of high temperature and high pressure, short reaction period and low energy consumption, is suitable for industrial popularization and application, and is superior to the prior methods.

Drawings

Fig. 1 is a scanning electron micrograph of a phyllostachys copper oxide nanosheet prepared in example 1;

FIG. 2 is a transmission electron micrograph of a phyllostachys copper oxide nanosheet prepared in example 1;

FIG. 3 is a scanning electron micrograph of large bamboo-leaf-shaped copper oxide nanoplates prepared in example 2;

FIG. 4 is a transmission electron micrograph of large bamboo-leaf-shaped copper oxide nanoplates prepared in example 2;

fig. 5 is a transmission electron microscope image of copper oxide nanoplates having no bamboo-leaf-like structure formed, prepared in comparative example 1;

FIG. 6 is a transmission electron micrograph of copper oxide particles prepared in comparative example 2 containing only a portion of bamboo-leaf-like structure;

fig. 7 is a transmission electron microscope image of copper oxide nanoplates having no bamboo-leaf-like structure formed, prepared in comparative example 3;

fig. 8 is a transmission electron microscope image of copper oxide nanoplates having no bamboo-leaf-like structure formed, prepared in comparative example 4.

Detailed Description

The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.

The preparation steps of the following examples 1-2 are the same and mainly comprise the following 5 steps:

step S1: dissolving a copper salt into a mixed solution of deionized water and ethanol in equal volume to prepare a solution A, and mixing sodium hydroxide and trisodium citrate in a ratio of 30: 1 is dissolved in deionized water to prepare solution B;

step S2: mixing the solution A and the solution B in proportion, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates;

step S3: heating the suspension C in mixed gas at 80-120 ℃ for 1.5h to obtain a black precipitate product, and cooling to room temperature;

step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates;

step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet.

Example 1

The preparation method comprises the following steps:

wherein the copper salt in S1 is copper nitrate, and the concentration of the copper salt in the solution A is 0.5 mol/L; the concentration of sodium hydroxide in the solution B is 0.3 mol/L;

the volume ratio of the solution A to the solution B in the S2 is 3: 1, stirring uniformly means stirring for 3min at 25 ℃, wherein the stirring speed is 300 rpm/min;

in the S3, the heating temperature is 90 ℃, the volume fraction of air in the mixed gas is 70%, and the volume fraction of oxygen is 30%;

the centrifugal washing frequency in the S4 is 2 times, each time is 1.5min, and the centrifugal speed is 4500 rpm/min;

and in S5, the drying environment is air atmosphere, 55 ℃ and 3 h.

The small bamboo leaf-shaped copper oxide sodium rice sheet with good dispersibility is prepared.

Fig. 1 and fig. 2 are a scanning electron microscope image and a transmission electron microscope image of the phyllostachys parquets copper oxide nanosheet prepared in example 1, respectively, and the phyllostachys parquets copper oxide nanosheet has good dispersibility, is 300-500 nm in length, and has the characteristics of wide middle part and narrow head.

Example 2

The preparation method comprises the following steps:

wherein the copper salt in the S1 is copper nitrate, and the concentration in the solution A is 0.5 mol/L; the concentration of sodium hydroxide in the solution B is 0.3 mol/L;

the volume ratio of the solution A to the solution B in the S2 is 3: 1; the stirring is uniform, namely stirring for 3min at 25 ℃, and the stirring speed is 300 rpm/min;

in the S3, the heating temperature is 110 ℃, the volume fraction of air in the mixed gas is 70%, and the volume fraction of oxygen is 30%;

the centrifugal washing frequency in the S4 is 2 times, each time is 1.5min, and the centrifugal speed is 4500 rpm/min;

and in S5, the drying environment is air atmosphere, 55 ℃ and 3 h.

The big bamboo leaf-shaped copper oxide sodium rice tablets with good dispersibility are prepared.

FIGS. 3 and 4 are a scanning electron microscope image and a transmission electron microscope image of the large bamboo leaf-shaped copper oxide nanosheet prepared in example 2, the dispersibility is good, the length is 500-1000 nm, and part of the nano-sheet has the characteristics of wide middle part and narrow head.

Comparative example 1

Step S1: dissolving a copper salt into a mixed solution of deionized water and ethanol in equal volume to prepare a solution A, and mixing sodium hydroxide and trisodium citrate in a ratio of 30: 1 is dissolved in deionized water to prepare solution B;

step S2: mixing the solution A and the solution B in proportion, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates;

step S3: heating the suspension C in mixed gas at 60 deg.C for 1.5h to obtain black precipitate, and cooling to room temperature;

step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates;

step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet.

The preparation method comprises the following steps:

wherein the copper salt in the S1 is copper nitrate, and the concentration in the solution A is 0.5 mol/L; the concentration of sodium hydroxide in the solution B is 0.3 mol/L;

the volume ratio of the solution A to the solution B in the S2 is 3: 1; the stirring is uniform, namely stirring for 3min at 25 ℃, and the stirring speed is 300 rpm/min;

in the S3, the volume fraction of air in the mixed gas is 70%, and the volume fraction of oxygen is 30%;

the centrifugal washing frequency in the S4 is 2 times, each time is 1.5min, and the centrifugal speed is 4500 rpm/min;

and in S5, the drying environment is air atmosphere, 55 ℃ and 3 h.

Fig. 5 is a transmission electron microscope image of copper oxide nanosheets formed with no bamboo-leaf-like structure prepared in comparative example 1, which nanosheets formed with no particular morphology.

Comparative example 2

Step S1: dissolving a copper salt into a mixed solution of deionized water and ethanol in equal volume to prepare a solution A, and mixing sodium hydroxide and trisodium citrate in a ratio of 30: 1 is dissolved in deionized water to prepare solution B;

step S2: mixing the solution A and the solution B in proportion, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates;

step S3: heating the suspension C in mixed gas at 140 deg.C for 1.5h to obtain black precipitate, and cooling to room temperature;

step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates;

step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet.

The preparation method comprises the following steps:

wherein the copper salt in the S1 is copper nitrate, and the concentration in the solution A is 0.5 mol/L; the concentration of sodium hydroxide in the solution B is 0.3 mol/L;

the ratio of solution a to solution B in S2 was 3: 1; stirring evenly means stirring for 3min at 25 ℃, and the stirring speed is 300 rpm/min;

the mixed gas in the S3 is 70 percent of air and 30 percent of oxygen;

the centrifugal washing frequency in the S4 is 2 times, each time is 1.5min, and the centrifugal speed is 4500 rpm/min;

and in S5, the drying environment is air atmosphere, 55 ℃ and 3 h.

FIG. 6 is a transmission electron microscope image of copper oxide particles prepared in comparative example 2, which only contain a part of bamboo leaf-shaped structures, wherein the shapes of the parts of the nano sheets are destroyed, and the bamboo leaf-shaped structures with uniform shapes cannot be obtained.

Comparative example 3

Step S1: dissolving copper salt into a mixed solution of deionized water and ethanol in equal volume to prepare a solution A, and dissolving sodium hydroxide into deionized water to prepare a solution B;

step S2: mixing the solution A and the solution B in proportion, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates;

step S3: heating the suspension C in mixed gas at 80-120 ℃ for 1.5h to obtain a black precipitate product, and cooling to room temperature;

step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates;

step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet.

The preparation method comprises the following steps:

wherein the copper salt in S1 is copper nitrate, and the concentration is 0.5 mol/L; the concentration of sodium hydroxide in the solution B is 0.3 mol/L;

the ratio of solution a to solution B in S2 was 3: 1; stirring evenly means stirring for 3min at 25 ℃, and the stirring speed is 300 rpm/min;

the mixed gas in the S3 is 70 percent of air and 30 percent of oxygen; the times of centrifugal washing are 2 times, each time is 1.5min, and the centrifugal speed is 4500 rpm/min; the drying environment is air atmosphere, 55 ℃, 3 h.

Fig. 7 is a transmission electron microscope image of copper oxide nanoplates having no bamboo-leaf-like structure formed, prepared in comparative example 3.

Comparative example 4

Step S1: dissolving copper salt into a mixed solution of deionized water and ethanol with equal volume to prepare a solution A, and mixing sodium hydroxide and N, N-dimethylformamide in a ratio of 30: 1 is dissolved in deionized water to prepare solution B;

step S2: mixing the solution A and the solution B in proportion, and uniformly stirring to obtain a suspension C with a large amount of blue precipitates;

step S3: heating the suspension C in mixed gas at 80-120 ℃ for 1.5h to obtain a black precipitate product, and cooling to room temperature;

step S4: respectively centrifugally washing the precipitated products by using deionized water and acetone in sequence, centrifuging after washing each time, and pouring out filtrate above precipitates;

step S5: drying and precipitating to obtain the bamboo leaf-shaped copper oxide nanosheet.

The preparation method comprises the following steps:

wherein the copper salt in S1 is copper nitrate, and the concentration is 0.5 mol/L; the concentration of sodium hydroxide in the solution B is 0.3 mol/L; the volume ratio of the solution A to the solution B is 3: 1;

stirring evenly in S2 means stirring for 3min at 25 ℃, wherein the stirring speed is 300 rpm/min;

in the S3, the volume fraction of air in the mixed gas is 70%, and the volume fraction of oxygen is 30%;

the centrifugal washing frequency in the S4 is 2 times, each time is 1.5min, and the centrifugal speed is 4500 rpm/min;

and in S5, the drying environment is air atmosphere, 55 ℃ and 3 h.

Fig. 8 is a transmission electron microscope image of copper oxide nanoplates having no bamboo-leaf-like structure formed, prepared in comparative example 4.

The difference between examples 1 and 2 and comparative examples 1 and 2 is only that the heating temperature is different (90 ℃, 110 ℃, 60 ℃ and 140 ℃), when the temperature is 90 ℃, the obtained bamboo leaf-shaped copper oxide nanosheets are 300-500 nm, and when the temperature is increased to 110 ℃, the size is changed to 500-1000 nm, so the temperature plays an important role in controlling the particle size. While comparative examples 1 and 2 exceed the lower limit and the upper limit of the temperature range specified in the present invention, respectively, and no bamboo leaf-like structure is formed, it can be seen from the above that an appropriate temperature range plays an important role in the formation of a bamboo leaf-like morphology.

Comparative examples 3 and 4 differ from the comparative examples of the other examples only in that no trisodium citrate was added as template (no addition of blank and addition of N, N-dimethylformamide, respectively), and no bamboo-leaf-like morphology was obtained, so that the template of trisodium citrate has a not negligible effect on the formation of bamboo-leaf-like morphology in addition to the appropriate temperature range.

It should be noted that, according to the implementation requirement, each step described in the present application can be divided into more steps, and two or more steps or partial operations of the steps can be combined into a new step to achieve the purpose of the present invention.

It should be understood that parts of the specification not set forth in detail are well within the prior art.

It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.