阅读说明：本技术 一种碳化铌纳米材料及其制备方法 (Niobium carbide nano material and preparation method thereof ) 是由 周海铃 陈怀俊 于 2021-03-23 设计创作，主要内容包括：本发明适用于纳米活性材料技术领域,提供了一种碳化铌纳米材料及其制备方法,该碳化铌纳米材料的制备方法包括以下步骤：以五氧化二铌为铌源,以丙酮、活性炭、石墨、石墨烯中的至少一种为碳源,将铌源、碳源和还原剂进行混合后,再进行微波辅助反应,得到反应粉末；将反应粉末置于酸溶液中进行酸浸后,再经干燥和过滤处理,得到所述碳化铌纳米材料。本发明实施例提供的制备方法,可以使五氧化二铌中氧逸出,然后通过在Nb晶体中逐渐加碳源而碳化还原形成NbC。本发明通过采用了微波辅助反应的方法,既可以大大降低反应所需温度,减少能源损耗,而且其制备的碳化铌纳米材料形貌粒径较均匀,易于进行表面功能化。(The invention is suitable for the technical field of nano active materials, and provides a niobium carbide nano material and a preparation method thereof, wherein the preparation method of the niobium carbide nano material comprises the following steps: mixing niobium pentoxide serving as a niobium source and at least one of acetone, activated carbon, graphite and graphene serving as a carbon source, and then carrying out microwave-assisted reaction to obtain reaction powder; and placing the reaction powder in an acid solution for acid leaching, and then drying and filtering to obtain the niobium carbide nano material. According to the preparation method provided by the embodiment of the invention, oxygen in niobium pentoxide can escape, and then the niobium pentoxide is carbonized and reduced to form NbC by gradually adding a carbon source into Nb crystals. The invention adopts the microwave-assisted reaction method, so that the temperature required by the reaction can be greatly reduced, the energy consumption is reduced, and the prepared niobium carbide nano material has uniform shape and particle size and is easy to carry out surface functionalization.)

1. The preparation method of the niobium carbide nano material is characterized by comprising the following steps of:

mixing niobium pentoxide serving as a niobium source and at least one of acetone, activated carbon, graphite and graphene serving as a carbon source, and then carrying out microwave-assisted reaction to obtain reaction powder;

and placing the reaction powder in an acid solution for acid leaching, and then drying and filtering to obtain the niobium carbide nano material.

2. The method for preparing the niobium carbide nano-material as claimed in claim 1, wherein the molar ratio of the niobium source to the carbon source is 1 (1-20).

3. The method for preparing the niobium carbide nano-material as claimed in claim 1, wherein the molar ratio of the niobium source to the reducing agent is 1 (1-10).

4. The method for preparing niobium carbide nano-material according to claim 1 or 3, wherein the reducing agent is at least one of magnesium, aluminum, zinc and iron.

5. The method for preparing niobium carbide nano-material according to claim 1, wherein the acid solution is a strong acid solution.

6. The method for preparing the niobium carbide nano material as claimed in claim 5, wherein the acid solution is a hydrochloric acid solution, and the mass percentage concentration of the hydrochloric acid solution is 40% -60%.

7. The method for preparing the niobium carbide nano-material as claimed in claim 1, wherein the temperature of the microwave-assisted reaction is 100 to 200 ℃, the microwave power is 500 to 1200W, and the microwave radiation frequency is 2400 to 2500 MHz.

8. A niobium carbide nano-material prepared by the preparation method of any one of claims 1 to 8.

9. The niobium carbide nanomaterial according to claim 8, wherein the particle size of the niobium carbide nanomaterial is 17-90 nm.

Technical Field

The invention belongs to the technical field of nano active materials, and particularly relates to a niobium carbide nano material and a preparation method thereof.

Background

With the high volume use of medical implants, medical implant-related infections are increasingly recognized as a troublesome global public health problem. Invading bacteria tend to rapidly adhere to the surface of the bioactive implant and form a biofilm, thereby surviving the hostile host environment. The polymeric matrix of the biofilm is resistant to penetration by antibiotics and immune cells and exhibits a great resistance compared to planktonic bacteria. Considering that biofilm formation is a major pathological feature of implant-related infections and bacterial attachment is a major cause of biofilm formation, extensive efforts have been made to develop implants containing antimicrobial agents. To date, these designs have primarily inhibited bacterial adhesion with limited impact on already formed biofilms. In addition, silver-resistant bacteria have been reported due to the long-term use of traditional antibacterial ions such as silver, which is a warning that traditional treatment regimens may induce resistance. In the absence of effective strategies in the development of antibacterial drugs and antibacterial films, innovative approaches inspired by the progress in the fields of nanomedicine and the like are increasingly favored by people to realize innovative antibacterial agents.

Mxene showed good antibacterial properties. Niobium carbide is one of the biodegradable mxenes. Niobium carbide has biodegradability of oxidative stress response, and is rich in H after sterilization₂O₂Gradually degrade in the Infectious Microenvironment (IME). Niobium carbide can inhibit the formation of a biological membrane by down-regulating a bacterial energy metabolism pathway, destroy the biological membrane by activating auxiliary gene regulation, and promote the shedding of the biological membrane, thereby directly eliminating bacteria. The temperature required to eradicate the bacteria is reduced and possible normal tissue damage is mitigated. Can eliminate excessive active oxygen in infection microenvironment, thereby relieving proinflammatory reaction.

It is reported that Li et al are a solid phase reaction process for the synthesis of niobium carbide by the chemical reaction of graphite-like and niobium pentoxide at 1150 ℃. Synthesizing niobium carbide powder through chemical reaction. And carbon nano tubes, niobium chloride and hydrogen are used as raw materials to synthesize the niobium carbide nano wires at 900 ℃.

The preparation methods of the niobium carbide nano materials have the defects of high reaction temperature, high raw material cost, high energy consumption, complex process, inconvenient operation and the like, and also have the problems of uneven morphology and particle size of the prepared nano particles and the like.

Disclosure of Invention

The embodiment of the invention aims to provide a preparation method of a niobium carbide nano material, aiming at solving the problems in the background technology.

The embodiment of the invention is realized in such a way that the preparation method of the niobium carbide nano material comprises the following steps:

mixing niobium pentoxide serving as a niobium source and at least one of acetone, activated carbon, graphite and graphene serving as a carbon source, and then carrying out microwave-assisted reaction to obtain reaction powder;

and placing the reaction powder in an acid solution for acid leaching, and then drying and filtering to obtain the niobium carbide nano material.

The graphene has a large contact area with niobium oxide in the reaction process, so that oxygen in a niobium pentoxide network structure is easily captured.

In a preferred embodiment of the present invention, the molar ratio of the niobium source to the carbon source is 1 (1-20).

In another preferred embodiment of the present invention, the molar ratio of the niobium source to the reducing agent is 1 (1-10).

As another preferable aspect of the embodiment of the present invention, the reducing agent is at least one of magnesium, aluminum, zinc, and iron.

As another preferable aspect of the embodiment of the present invention, the reducing agent is magnesium.

As another preferable mode of the embodiment of the present invention, the acid solution is a strong acid solution such as hydrochloric acid, nitric acid, sulfuric acid, and the like.

As another preferable scheme of the embodiment of the invention, the acid solution is a hydrochloric acid solution, and the mass percentage concentration of the acid solution is 40-60%.

As another preferable scheme of the embodiment of the invention, the temperature of the microwave-assisted reaction is 100-200 ℃, the microwave power is 500-1200W, and the microwave radiation frequency is 2400-2500 MHz.

Another object of an embodiment of the present invention is to provide a niobium carbide nanomaterial prepared by the above preparation method.

As another preferable scheme of the embodiment of the invention, the particle size of the niobium carbide nano material is 17-90 nm.

According to the preparation method of the niobium carbide nano material provided by the embodiment of the invention, oxygen in niobium pentoxide can escape, and then the niobium pentoxide is carbonized and reduced to form NbC by gradually adding a carbon source into Nb crystals. The invention adopts the microwave-assisted reaction method, can greatly reduce the temperature required by the reaction and reduce the energy consumption, has the characteristics of lower reaction temperature, low raw material cost, low energy consumption, simple process, simple and convenient operation and the like, and the prepared niobium carbide nano material has uniform shape and particle size, is easy to carry out surface functionalization and can be widely applied to the field of biomedicine.

Drawings

FIG. 1 is a TEM image of the niobium carbide nanomaterial prepared in example 1 of the present invention.

FIG. 2 is a TEM image of the surface-functionalized niobium carbide nanomaterial prepared in example 1 of the present invention.

FIG. 3 is a TEM image of the Nb carbide nanomaterial prepared in example 2 of the present invention.

FIG. 4 is a TEM image of the surface-functionalized niobium carbide nanomaterial prepared in example 2 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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.

In addition, those whose specific conditions are not specified in the examples are conducted under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

Example 1

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, mixing 1mmol of niobium source, 10mmol of carbon source and 5mmol of reducing agent by taking niobium pentoxide as niobium source, acetone as carbon source and magnesium as reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃ for microwave-assisted reaction for 6 hours, and simultaneously carrying out mechanical stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material; the particle size of the niobium carbide nano material is 90nm, and a TEM image of the niobium carbide nano material is shown in figure 1. In addition, according to the conventional method in the prior art, the surface of the niobium carbide nano material is loaded with amino (-NH)₂) After the functional group, its TEM image is shown in fig. 2. As can be seen from FIGS. 1 and 2, the niobium carbide nanomaterial prepared by the embodiment of the invention has uniform morphology and particle size, and is easy to carry other functional groups on the surface for functional modification.

Example 2

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, mixing 1mmol of niobium source, 10mmol of carbon source and 5mmol of reducing agent by taking niobium pentoxide as niobium source, activated carbon as carbon source and magnesium as reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃ for microwave-assisted reaction for 6 hours, and simultaneously mechanically stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material; the particle size of the niobium carbide nano material is 17nm, and a TEM image of the niobium carbide nano material is shown in an attached figure 3. In addition, according to the conventional method of the prior art, after the surface of the niobium carbide nanomaterial is loaded with a carboxyl (-COOH) functional group, a TEM image thereof is shown in fig. 4. As can be seen from FIGS. 3 and 4, the niobium carbide nanomaterial prepared by the embodiment of the invention has uniform morphology and particle size, and is easy to carry other functional groups on the surface for functional modification.

Example 3

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, mixing 1mmol of niobium source, 1mmol of carbon source and 1mmol of reducing agent by taking niobium pentoxide as a niobium source, graphite as a carbon source and aluminum as a reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 100 ℃, carrying out microwave-assisted reaction for 0.5h, and simultaneously carrying out mechanical stirring to obtain reaction powder; wherein the microwave power is 500W, and the microwave radiation frequency is 2400 MHz.

S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 40% for acid leaching for 1h, and then drying and filtering to obtain the niobium carbide nano material.

Example 4

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, mixing 1mmol of niobium source, 20mmol of carbon source and 10mmol of reducing agent by taking niobium pentoxide as niobium source, graphene as carbon source and zinc as reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 200 ℃ for microwave-assisted reaction for 12 hours, and simultaneously mechanically stirring to obtain reaction powder; wherein the microwave power is 1200W, and the microwave radiation frequency is 2500 MHz.

S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 60% for acid leaching for 48 hours, and then drying and filtering to obtain the niobium carbide nano material.

Example 5

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, taking niobium pentoxide as a niobium source, taking a mixture of acetone and activated carbon in an equal molar ratio as a carbon source, taking iron as a reducing agent, mixing 1mmol of niobium source, 2mmol of carbon source and 2mmol of reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃ for microwave-assisted reaction for 6 hours, and simultaneously mechanically stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

And S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material.

Example 6

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, taking niobium pentoxide as a niobium source, taking a mixture of graphite and graphene in an equimolar ratio as a carbon source, taking a mixture of zinc and iron in an equimolar ratio as a reducing agent, mixing 1mmol of niobium source, 15mmol of carbon source and 5mmol of reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃ for microwave-assisted reaction for 6 hours, and simultaneously mechanically stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

And S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material.

Example 7

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, taking niobium pentoxide as a niobium source, taking a mixture of activated carbon, graphite and graphene in an equimolar ratio as a carbon source, taking a mixture of magnesium, aluminum and zinc in an equimolar ratio as a reducing agent, mixing 1mmol of niobium source, 18mmol of carbon source and 3mmol of reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃, performing microwave-assisted reaction for 6 hours, and simultaneously performing mechanical stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

And S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material.

Example 8

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, taking niobium pentoxide as a niobium source, taking a mixture of acetone and graphene in an equimolar ratio as a carbon source, taking a mixture of magnesium and aluminum in an equimolar ratio as a reducing agent, mixing 1mmol of niobium source, 10mmol of carbon source and 2mmol of reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃ for microwave-assisted reaction for 6 hours, and simultaneously mechanically stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

And S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material.

Example 9

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, mixing 1mmol of niobium source, 12mmol of carbon source and 3mmol of reducing agent by taking niobium pentoxide as niobium source, graphene as carbon source and magnesium as reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃ for microwave-assisted reaction for 6 hours, and simultaneously carrying out mechanical stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

And S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material.

Example 10

The embodiment provides a preparation method of a niobium carbide nano material, which comprises the following steps:

s1, taking niobium pentoxide as a niobium source, taking a mixture of activated carbon and graphene in an equimolar ratio as a carbon source, taking magnesium as a reducing agent, mixing 1mmol of niobium source, 15mmol of carbon source and 8mmol of reducing agent, placing the mixture in a microwave oven reaction kettle, heating to 150 ℃ for microwave-assisted reaction for 6 hours, and simultaneously mechanically stirring to obtain reaction powder; wherein the microwave power is 800W, and the microwave radiation frequency is 2450 MHz.

And S2, placing the reaction powder in a hydrochloric acid solution with the mass percentage concentration of 50% for acid leaching for 24 hours, and then drying and filtering to obtain the niobium carbide nano material.

In summary, the preparation method of the niobium carbide nanomaterial provided by the embodiment of the invention can allow oxygen in niobium pentoxide to escape, and then gradually add a carbon source into Nb crystals to carbonize and reduce the niobium pentoxide to form NbC. The invention adopts the microwave-assisted reaction method, can greatly reduce the temperature required by the reaction and reduce the energy consumption, has the characteristics of lower reaction temperature, low raw material cost, low energy consumption, simple process, simple and convenient operation and the like, and the prepared niobium carbide nano material has uniform shape and particle size, is easy to carry out surface functionalization and can be widely applied to the field of biomedicine.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.