阅读说明：本技术 一种红色氮化碳宽光谱响应光催化剂的制备方法及产品 (Preparation method of red carbon nitride wide-spectral-response photocatalyst and product ) 是由 贾长超 高爱林 刘文刚 万冰洁 王志远 于 2021-09-26 设计创作，主要内容包括：本发明公开了一种红色氮化碳宽光谱响应材料的制备方法及产品,方法步骤包括：使用胍和氰胺作为原料,乙腈作为溶剂,经充分混合后进行溶剂热处理,随后将离心洗涤后的产物与三聚氰胺混合研磨,进行热聚合反应,最终制得红色氮化碳宽光谱响应的材料。本发明解决了氮化碳样品对于可见光吸收利用率低的问题,将氮化碳的光吸收响应范围从传统的可见光区拓展至近红外光区,充分利用了太阳光能,并且制备的红色氮化碳材料在光催化能源环境以及医疗等领域具有潜在的应用价值。(The invention discloses a preparation method and a product of a red carbon nitride wide-spectrum response material, wherein the method comprises the following steps: guanidine and cyanamide are used as raw materials, acetonitrile is used as a solvent, solvent heat treatment is carried out after full mixing, and then products after centrifugal washing and melamine are mixed and ground for thermal polymerization reaction, and finally the red carbon nitride broad-spectrum response material is prepared. The method solves the problem of low visible light absorption utilization rate of the carbon nitride sample, expands the light absorption response range of the carbon nitride from the traditional visible light region to the near infrared light region, fully utilizes solar energy, and has potential application value in the fields of photocatalytic energy environment, medical treatment and the like.)

1. A preparation method of a red carbon nitride broad-spectrum response material and a product thereof are characterized by comprising the following specific steps:

(1) firstly, dissolving guanidine and cyanamide in an acetonitrile solvent, fully mixing, and then carrying out solvent heat treatment;

(2) and mixing the centrifugally washed product with melamine, fully grinding, and carrying out thermal polymerization reaction to finally prepare the red carbon nitride broad-spectrum response material.

2. The method of claim 1, wherein: in the step (1), the guanidine is guanidine hydrochloride or guanidine carbonate.

3. The method of claim 1, wherein: in the step (1), the cyanamide is cyanamide or dicyandiamide.

4. The method of claim 1, wherein: in the step (1), the molar ratio of guanidine to cyanamide is 1: 1.

5. The method of claim 1, wherein: in the step (1), the total molar concentration of guanidine and cyanamide dissolved in acetonitrile is as follows: 0.01 to 1 mol/L.

6. The method of claim 1, wherein: in the step (1), the temperature is 160-220 ℃, and the time is 24-72 hours.

7. The method of claim 1, wherein: in the step (2), the mass ratio of the product to the melamine is 1:1 to 5.

8. The method of claim 1, wherein: in the step (2), the thermal polymerization calcination temperature is 600-750 ℃, and the heating rate is 1-5 ℃ for min^-1The time is 1-10 h.

Technical Field

The invention belongs to the technical field of preparation of photocatalytic materials, and relates to a preparation method of a red carbon nitride wide-spectrum response material.

Background

The polymer semiconductor carbon nitride material is widely researched as a metal-free semiconductor material due to its environmental friendliness, low cost, good chemical stability and appropriate band gap width in a visible light region. The material has excellent physical, chemical and optical properties, so that the material has extremely high research value in the fields of photocatalysis, sensing, solar cells, ion transmission and the like. However, the carbon nitride material is usually prepared by high-temperature thermal polymerization of nitrogen-rich precursors (dicyandiamide, melamine, cyanuric acid, urea, etc.), the obtained sample is light yellow, the photoresponse range is mainly concentrated in a visible light region, the utilization rate of light is low, and the current requirements of people are difficult to meet. In recent years, researchers strive to widen the photoresponse range of materials by means of metal or nonmetal doping and compounding with other semiconductor materials, but the expansion of the photoresponse range of single carbon nitride materials to the near infrared region has higher challenges and has fewer related reports at present.

Disclosure of Invention

Aiming at the problems that the light absorption range of a normally synthesized light yellow carbon nitride material is mainly concentrated in a visible light region and the light utilization rate is not high, the invention prepares the photocatalyst with the wide spectral response of red carbon nitride. The invention prepares the red carbon nitride photocatalyst material with wide spectral response, and the photoresponse range of which can be expanded to a near-infrared region, by combining a solvothermal method and a calcination method. The carbon nitride material has the advantages of stable chemical property, environmental friendliness, no toxicity, no metal element and the like, so the material has potential application value in the fields of photocatalysis, biomedical treatment and the like.

The technical scheme of the invention is as follows:

a preparation method of a red carbon nitride broad-spectrum response material and a product thereof are characterized by comprising the following specific steps:

(1) firstly, dissolving guanidine and cyanamide in an acetonitrile solvent, fully mixing, and then carrying out solvent heat treatment;

(2) and mixing the centrifugally washed product with melamine, fully grinding, and carrying out thermal polymerization reaction to finally prepare the red carbon nitride broad-spectrum response material.

In the step (1), the guanidine is guanidine hydrochloride or guanidine carbonate.

In the step (1), the cyanamide is cyanamide or dicyandiamide.

In the step (1), the molar ratio of guanidine to cyanamide is 1: 1.

In the step (1), the total molar concentration of guanidine and cyanamide dissolved in acetonitrile is: 0.01 to 1 mol/L.

In the step (1), the temperature is 160-220 ℃ and the time is 24-72 hours.

In the step (2), the mass ratio of the product to the melamine is 1:1 to 5.

In the step (2), the thermal polymerization calcination temperature is 600-750 ℃, and the heating rate is 1-5 ℃ for min^-1The time is 1-10 h.

The invention introduces a preparation method of a red carbon nitride wide-spectral response photocatalyst material, which has the following beneficial effects: the method has the advantages of simple and convenient operation process, low cost and high application value, expands the photoresponse range of the common light yellow carbon nitride material from a visible light region to a near infrared light region, not only improves the utilization rate of the material to light, but also can expand the wide application of the material in the fields of near infrared light responsive photocatalysis, biological medicine and the like.

Drawings

FIG. 1 is a Transmission Electron Microscope (TEM) photograph of a red carbon nitride material synthesized in example 1 of the present invention.

FIG. 2 is an X-ray diffraction (XRD) pattern of a red carbon nitride material synthesized in example 1 of the present invention.

FIG. 3 shows the Diffuse Reflectance Spectrum (DRS) of the red carbon nitride material synthesized in example 1 of the present invention and the Diffuse Reflectance Spectrum (DRS) of the yellow carbon nitride material synthesized in comparative example 1.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

For a further understanding of the invention, reference will now be made to the following description taken in conjunction with the accompanying drawings and examples.

Example 1

1.1, dissolving 2.28g of guanidine hydrochloride and 2g of dicyandiamide in 60mL of acetonitrile solution, fully mixing and uniformly stirring, and then carrying out solvent thermal reaction for 48h at 180 ℃;

1.2 the centrifuged product (0.3g) after the reaction described in 1.1 was mixed by grinding with 1.2g of melamine at 2 ℃ for min^-1The temperature is raised to 650 ℃ at the temperature raising rate, the temperature is kept for 2h under the inert atmosphere, the obtained sample is a red carbon nitride broad-spectrum response material, a transmission electron microscope photo of the sample is shown in figure 1, the components and the structure of the sample are shown in figure 2, and a diffuse reflection spectrum is shown in figure 3.

Example 2

2.1 dissolving 1.14g of guanidine hydrochloride and 1g of dicyandiamide in 60mL of acetonitrile solution, fully mixing and stirring uniformly, and then carrying out solvent thermal reaction at 180 ℃ for 24 h;

2.2 grinding and mixing the centrifuged product (0.3g) obtained after the reaction described in 2.1 with 1.2g of melamine, at 2 ℃ for min^-1The temperature is raised to 650 ℃ and kept for 2h under inert atmosphere, and the obtained sample is a red carbon nitride broad-spectrum response material.

Example 3

3.1 dissolving 0.285g of guanidine hydrochloride and 0.25g of dicyandiamide in 60mL of acetonitrile solution, fully mixing and stirring uniformly, and then carrying out solvent thermal reaction for 72h at 180 ℃;

3.2 grinding and mixing the centrifuged product (0.3g) after the reaction described in 3.1 with 1.2g of melamine, at 2 ℃ for min^-1The temperature is raised to 650 ℃ and kept for 2h under inert atmosphere, and the obtained sample is a red carbon nitride broad-spectrum response material.

Example 4

4.1 dissolving 1.14g of guanidine carbonate and 2g of cyanamide in 60mL of acetonitrile solution, fully mixing and stirring uniformly, and then carrying out solvent thermal reaction at 180 ℃ for 48 h;

4.2 grinding and mixing the centrifuged product (0.3g) after the reaction described in 4.1 with 1.5g of melamine, at 2 ℃ for min^-1The temperature rise rate of the temperature rise is up to 750 DEG CAnd preserving the heat for 1h in an inert atmosphere, wherein the obtained sample is a red carbon nitride broad-spectrum response material.

Example 5

5.1 dissolving 1.14g of guanidine carbonate and 2g of cyanamide in 60mL of acetonitrile solution, fully mixing and stirring uniformly, and then carrying out 160 ℃ solvothermal reaction for 72 h;

5.2 grinding and mixing the centrifuged product (0.3g) obtained after the reaction described in 5.1 with 0.3g of melamine at 2 ℃ for min^-1The temperature is raised to 600 ℃ and kept for 10h under inert atmosphere, and the obtained sample is a red carbon nitride broad-spectrum response material.

Comparative example 1

Weighing 3g of dicyandiamide and 15g of ammonium chloride, fully and uniformly mixing, and then placing in a tube furnace at 2.5 ℃ for min^-1Raising the temperature to 550 ℃ at a speed, and preserving the temperature for 4h to prepare the carbon nitride nanosheet, wherein the diffuse reflection spectrum of the yellow sample of the carbon nitride nanosheet is shown in figure 3.

Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or modification made within the spirit and principle of the present invention should be included in the protection scope of the present invention.