阅读说明：本技术 表面褶皱氮化碳材料的制备方法 (Preparation method of surface-wrinkled carbon nitride material ) 是由 姜炜 李东楠 谈玲华 郝嘎子 胡玉冰 肖磊 柯香 黎博 李蔡伟 于 2018-08-06 设计创作，主要内容包括：本发明公开了一种表面褶皱氮化碳材料的制备方法。所述方法充分研磨的g-C<Sub>3</Sub>N<Sub>4</Sub>粉末置于氢氧化钠溶液中分散,然后在60±10℃下搅拌反应,反应期间进行间断超声处理,反应结束后透析除去多余氢氧化钠,离心得到表面褶皱氮化碳材料。本发明方法制备的g-C<Sub>3</Sub>N<Sub>4</Sub>材料经过改性后具有褶皱形貌,具有更大的比表面积,释放更多活性位点,在高氯酸铵热分解中表现出更好的催化效果,使高氯酸铵热分解的高温分解峰从原来的443℃大幅提前到338℃。(The invention discloses a preparation method of a surface-wrinkled carbon nitride material. Said process fully milled g-C 3 N 4 And (3) dispersing the powder in a sodium hydroxide solution, then stirring and reacting at 60 +/-10 ℃, carrying out intermittent ultrasonic treatment during the reaction, dialyzing to remove excessive sodium hydroxide after the reaction is finished, and centrifuging to obtain the surface-wrinkled carbon nitride material. g-C prepared by the process of the invention 3 N 4 The modified material has a fold shape, has a larger specific surface area, releases more active sites, shows a better catalytic effect in the thermal decomposition of ammonium perchlorate, and greatly advances the pyrolysis peak of the thermal decomposition of ammonium perchlorate from 443 ℃ to 338 ℃.)

1. The preparation method of the surface-wrinkled carbon nitride material is characterized by comprising the following steps of:

and (2) placing the graphite-phase carbon nitride powder in 1-3 mol/L sodium hydroxide solution, stirring and reacting at 60 +/-10 ℃, carrying out intermittent ultrasonic treatment in the reaction process, dialyzing after the reaction is finished, removing the residual sodium hydroxide, adding water for diluting, carrying out ultrasonic dispersion, centrifuging, and drying to obtain the surface-wrinkled carbon nitride material.

2. The preparation method according to claim 1, wherein the reaction time is 6-12 h.

3. The preparation method according to claim 1, wherein the interval time is 2-4 h and the ultrasonic dispersion time is 0.5-1 h in the intermittent ultrasonic treatment process.

4. The preparation method according to claim 3, wherein the ultrasonic dispersion time is 10-20 min.

5. The method according to claim 1, wherein the centrifugation is performed at 9000 to 10000rpm for 10 to 15 min.

Technical Field

The invention belongs to the technical field of energetic material preparation, and relates to surface-wrinkled carbon nitride (sfg-C)₃N₄) A method for preparing the material.

Background

Graphite phase carbon nitride (g-C)₃N₄) As a novel inorganic non-metal semiconductor, the catalyst has good thermal stability, acid and alkali resistance and chemical stability, and has wide application prospect in the field of catalysis. Furthermore, g-C₃N₄The preparation process is simple, has no metal elements, has low cost and is beneficial to realizing industrial production. However, g-C prepared by conventional thermal polycondensation₃N₄The specific surface area is small and is 8.0m²/g(Wang K,Li Q,Liu B,et al.Sulfur-doped g-C₃N₄withenhanced photocatalytic CO2-reduction performance[J]Applied Catalysis B: Environmental,2015,176: 44-52.). Too low a specific surface area results in fewer exposed active sites and inhibits catalytic activity, so researchers have used a series of modification methods to increase g-C₃N₄And certain achievements are achieved, such as structural modification, morphology control, element doping, semiconductor coupling and the like. Particularly in the aspect of shape control, the shape of the catalyst represents an exposed crystal face, and the size of the specific surface area and the number of active sites are influenced, so that the shape is one of the key factors influencing the catalytic performance of the material. Thus synthesizing g-C with special morphology₃N₄Has great significance in the field of catalysis.

Ammonium Perchlorate (AP) is a commonly used oxidizer in solid composite propellants and also is a high-energy component of the solid composite propellants, the proportion of the Ammonium Perchlorate (AP) in the propellants is about 70 percent, and the thermal decomposition characteristic of the Ammonium Perchlorate (AP) is one of important factors influencing the combustion performance of the propellants. Researches show that most of metal simple substances, metal oxides and compounds thereof have catalytic effect on the thermal decomposition of ammonium perchlorate, and can reduce the activation energy of the decomposition of the ammonium perchlorate and improve the thermal decomposition rate of the ammonium perchlorate. But the environmental-friendly inorganic non-metal catalyst g-C is considered from the aspects of environmental protection and cost reduction₃N₄In the presence of a catalytic amine perchlorateHas attracted extensive attention, wherein g-C with special morphology is synthesized₃N₄It is an important direction to increase the specific surface area and active sites thereof to improve the catalytic effect on ammonium perchlorate.

Disclosure of Invention

The invention aims to provide a preparation method of a carbon nitride material with surface wrinkles. The method takes graphite phase carbon nitride as a raw material, modifies the raw material by sodium hydroxide solution and is assisted by ultrasonic treatment to prepare the surface fold carbon nitride (sfg-C) with larger specific surface area and more active sites₃N₄)。

In order to achieve the purpose, the technical scheme of the invention is as follows:

the preparation method of the surface-wrinkled carbon nitride material comprises the following steps:

and (2) placing the graphite-phase carbon nitride powder in 1-3 mol/L sodium hydroxide solution, stirring and reacting at 60 +/-10 ℃, carrying out intermittent ultrasonic treatment in the reaction process, dialyzing after the reaction is finished, removing the residual sodium hydroxide, adding water for diluting, carrying out ultrasonic dispersion, centrifuging, and drying to obtain the surface-wrinkled carbon nitride material.

Preferably, the reaction time is 6-12 h, the interval time is 2-4 h and the ultrasonic dispersion time is 0.5-1 h in the intermittent ultrasonic treatment process.

Preferably, the ultrasonic dispersion time is 10-20 min.

Preferably, the rotating speed of the centrifugation is 9000-10000 rpm, and the centrifugation time is 10-15 min.

Compared with the prior art, the invention has the following advantages:

using sodium hydroxide solution for g-C₃N₄The modification and the auxiliary ultrasonic treatment are carried out, so that the flat surface of the material becomes wrinkled and the block-shaped material becomes flaky, the material obtains larger specific surface area and more active centers, the effect of catalyzing the thermal decomposition of the ammonium perchlorate is effectively improved, and the pyrolysis peak of the thermal decomposition of the ammonium perchlorate is greatly advanced from 443 ℃ to 338 ℃ and is advanced by 105 ℃.

Drawings

FIG. 1 shows sfg-C prepared in example 1₃N₄And g-C₃N₄XRD profile of (a).

In FIG. 2, g-C₃N₄(a) SEM images of comparative example 1(b), example 1(c), example 2(d), example 3(e) and comparative example 2 (f).

FIG. 3 is g-C₃N₄sfg-C from example 1, comparative example 2₃N₄Thermal decomposition profile of catalytic ammonium perchlorate.

Detailed Description

The invention is further described below with reference to examples and figures. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.