阅读说明：本技术 一种偶蹄目动物蹄甲衍生碳量子点的制备方法 (Preparation method of artiodactyla animal hoof nail derived carbon quantum dots ) 是由 李俊锋 李美玲 于 2020-12-15 设计创作，主要内容包括：本发明涉及一种碳量子点制备领域,提供了一种偶蹄目动物蹄甲衍生碳量子点及其制备方法。本发明提供的偶蹄目动物蹄甲衍生碳量子点的制备方法,包括以下步骤：将偶蹄目动物蹄甲洗涤干燥后,用粉碎机粉碎,再将偶蹄目动物蹄甲粉末与弱碱盐、水混合后烘干,得到混合物；再将上述所提及的混合物置于管式炉中进行煅烧活化得到活化产物；所述活化产物浸泡于酸性溶液中,洗涤至中性后干燥,得到偶蹄目动物蹄甲衍生碳；再将其置于强氧化性溶剂中进行加热回流,回流后调节溶液pH至中性,过滤、透析和冷冻干燥后得到偶蹄目动物蹄甲衍生碳量子点。本发明以廉价易得的偶蹄目动物蹄甲为原料制备碳量子点,制备方法简单,量子产率高。(The invention relates to the field of carbon quantum dot preparation, and provides artiodactyla animal hoof nail derived carbon quantum dots and a preparation method thereof. The invention provides a preparation method of artiodactyla animal hoof derived carbon quantum dots, which comprises the following steps: washing and drying artiodactyla hooves, crushing by a crusher, mixing the artiodactyla hooves powder with weak alkali salt and water, and drying to obtain a mixture; then placing the mixture into a tubular furnace for calcination and activation to obtain an activated product; soaking the activated product in an acid solution, washing to neutrality, and drying to obtain artiodactyla animal hoof nail derived carbon; and then placing the mixture into a strong oxidizing solvent for heating reflux, adjusting the pH of the solution to be neutral after reflux, filtering, dialyzing and freeze-drying to obtain the artiodactyla animal hoof nail derived carbon quantum dots. The invention takes cheap and easily obtained artiodactyla animal hooves as raw materials to prepare the carbon quantum dots, the preparation method is simple, and the quantum yield is high.)

1. A preparation method of artiodactyla derived carbon quantum dots is characterized by comprising the following steps:

washing and drying the artiodactyla hooves, crushing and sieving to prepare powder of the artiodactyla hooves; sieving the obtained artiodactyla powder with 10-20 mesh sieve;

uniformly mixing the obtained artiodactyla animal hoof powder with alkalescent salt and water, and drying to obtain a mixture; the mass ratio of the artiodactyla powder to the weak base salt is 1: (0.1-4);

calcining the mixture in a tubular furnace to obtain an activated sample, adding acid to the activated sample for soaking, washing for a plurality of times, and drying to obtain artiodactyla hoof nail derived carbon;

placing the artiodactyla hoof nail derived carbon in a strong oxidizing solvent, heating and refluxing, cooling to room temperature, adjusting the pH of the solution to 7, filtering, dialyzing the filtrate, and freeze-drying to obtain the artiodactyla hoof nail derived carbon quantum dots;

wherein the alkalescent salt is Na₂CO₃、NaHCO₃、K₂CO₃、KHCO₃In the preparation of the artiodactyla hoof-derived carbon, the impregnated sample is carbonized at the temperature of 600-900 ℃ for 0.5-4 h.

2. The method for preparing artiodactyla hoof-derived carbon quantum dots according to claim 1, wherein the filtrate is dialyzed with a dialysis bag with molecular weight cut-off of 500-2000 Da.

3. The artiodactyla ungula-derived carbon quantum dots are obtained by the preparation method of claims 1-2.

4. The artiodactyl hoof-derived carbon quantum dots of claim 3, wherein the grain size of the artiodactyl hoof-derived carbon quantum dots is 1-10 nm.

Technical Field

The invention belongs to the technical field of carbon quantum dot preparation, and particularly relates to a preparation method of artiodactyla animal hoof nail derived carbon quantum dots.

Background

The carbon quantum dots are multifunctional spherical nano materials with the diameter less than 10 nanometers. Since the discovery in 2004, carbon quantum dots have been widely used in the fields of biomedicine, photoelectron, catalysis, sensors, etc. due to their characteristics of easy synthesis, low cytotoxicity, good water solubility, high chemical inertness, etc.

At present, raw materials adopted by the prepared carbon quantum dots are all non-renewable resources, and the processing procedures of the raw materials are complex, so that the preparation cost of the carbon quantum dots is greatly increased. Therefore, it is important to adopt easily available, cheap, non-toxic, harmless and environment-friendly raw materials, and the preparation of carbon quantum dots by using the raw materials also draws more and more attention of people.

Compared with the traditional fluorescent material, the carbon quantum dot has good light stability, photobleaching resistance, tunable excitation and emission spectrum and good biocompatibility. However, the preparation process of the carbon quantum dots has the problems of complex process, expensive raw materials and the like in the prior art. In order to solve the problems in the preparation process, the invention aims to provide a process method for simply preparing artiodactyla animal hoof derived carbon quantum dots. The method has the characteristics of simple preparation method, cheap and easily-obtained raw materials, uniform particle size distribution of the prepared carbon quantum dots and the like.

Disclosure of Invention

In order to solve the technical problems, the technical scheme of the invention is as follows:

in order to solve the problems in the prior synthesis technology, the invention aims to provide a preparation method of artiodactyla animal hoof nail derived carbon quantum dots, so as to solve the problems of high cost of raw materials, complex process and the like in the prior art.

The technical scheme for solving the technical problems is as follows:

a preparation method of artiodactyla hoof derived carbon quantum dots comprises the following steps:

washing and drying the artiodactyla hooves, and then crushing and grinding the washed and dried artiodactyla hooves to obtain artiodactyla hooves powder;

then mixing the artiodactyla powder with weakly alkaline salt and water, and drying to obtain a mixture;

then uniformly mixing the mixture and an activating agent, activating, and placing the mixture in a tubular furnace for calcining to obtain an activated product;

further soaking the activated product in an acid solution, washing and drying to obtain artiodactyla animal hoof nail derived carbon;

dissolving the artiodactyla derived carbon in a strong oxidizing solvent, heating and refluxing, cooling to room temperature, adjusting the pH of the solution to be neutral, filtering, dialyzing, freezing and drying to finally obtain the artiodactyla derived carbon quantum dots;

wherein the activating agent is KOH or K₂CO₃、KHCO₃One or more of (a).

The activation temperature is 600-900 ℃, the temperature is increased from room temperature to the activation temperature at the speed of 2-5 ℃/min, and the heat preservation time is 0.5-3h after the temperature is increased to the activation temperature.

The acidic solution is preferably dilute hydrochloric acid, dilute sulfuric acid and dilute phosphoric acid, and the concentration of the acidic solution is 0.5-1 mol/L.

The strongly oxidizing solvent is preferably nitric acid, sulfuric acid, having a concentration of 2 to 6mol/L, and a hydrogen peroxide solution, having a concentration of 10 to 30%.

The reflux heating temperature is 80-160 ℃, and the reflux heating time is 2-7 h.

The pH adjusting solution is preferably sodium hydroxide and sodium bicarbonate, and the concentration of the pH adjusting solution is 0.1-1 mol/L.

The invention also provides the artiodactyl ungula derived carbon quantum dots prepared by the method in the technical scheme, the artiodactyl ungula derived carbon quantum dots are amorphous carbon, the artiodactyl ungula derived carbon quantum dots contain carbon, hydrogen, nitrogen and other elements, and the artiodactyl ungula derived carbon quantum dots have good fluorescence.

The invention provides a preparation method of artiodactyla animal hoof nail derived carbon quantum dots, which comprises the following steps: washing, drying, crushing and grinding the artiodactyla hooves, mixing with weak base salt and water, and drying to obtain a mixture; activating the mixture at high temperature to obtain an activated product; soaking the activated product prepared in the step in an acid solution, washing to be neutral, and drying to obtain artiodactyla animal hoof nail derived carbon; and then placing the artiodactyla animal hoof nail derived carbon in a strong oxidizing solvent for heating and refluxing, cooling to room temperature, adjusting the pH value to be neutral, filtering, dialyzing, freezing and drying to finally obtain the artiodactyla animal hoof nail derived carbon quantum dots. The artiodactyla hooves are generally discarded as waste as accessories of the artiodactyla, and the artiodactyla hooves are rich in protein, contain rich elements such as carbon, nitrogen and oxygen, and can cause environmental pollution and resource waste when directly discarded. The invention takes cheap and easily available artiodactyla hoof nail as a raw material to prepare the artiodactyla hoof nail derived carbon quantum dots, and the preparation method is simple, easy to operate, high in repetition rate and excellent in fluorescence performance.

Drawings

FIG. 1 is a Fourier transform infrared (FT-IR) spectrum of a pig nail powder obtained by washing, pulverizing, sieving, and drying in an oven at 60 ℃ in example 1

FIG. 2 is an X-ray diffraction (XRD) pattern of pig nail-derived carbon obtained in example 1

FIG. 3 is a Fourier transform infrared (FT-IR) spectrum of pig nail derived carbon quantum dots obtained in example 1

FIG. 4 shows fluorescence spectra of pig nail derived carbon quantum dots obtained in example 1 at different excitation wavelengths

Detailed Description

The principles and features of the present invention will be described in conjunction with the accompanying drawings, which are provided as examples to illustrate the invention and are not limited to practice with pigs, cattle, sheep. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The chemical reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

Working example 1

Washing, crushing and sieving the pig nail, drying in an oven at 60 ℃, and preparing pig nail powder according to the mass ratio: KOH 1: 2 adding a proper amount of water, mixing, and drying at 85 ℃ to obtain an impregnated sample. And (3) putting the impregnated sample into a tube furnace, and carbonizing at 700 ℃ for 2h to obtain a carbonized sample. Grinding the carbonized sample, weighing 0.1g of the carbonized sample, adding a proper amount of water, soaking and stirring, adding a certain amount of hydrogen peroxide solution into the suspension, and placing the suspension in an oil bath kettle at 120 ℃ for stirring for 10 hours. After the reaction is finished, filtering the solution by using a filter head, and dialyzing the filtrate for 24 hours by using a 1000Da dialysis bag to obtain a light yellow carbon quantum dot aqueous solution. The carbon quantum dot aqueous solution is kept still for more than 3 weeks, no insoluble substances are separated out, and the fluorescence intensity is basically kept unchanged.

And (3) freeze-drying the pig nail derived carbon quantum dot aqueous solution to obtain the pig nail derived carbon quantum dot.

Example 2

Washing, crushing and sieving the pig nail, drying in an oven at 60 ℃, and preparing pig nail powder according to the mass ratio: k₂CO₃1: 3 adding a proper amount of water, mixing, and drying at 85 ℃ to obtain a dipping sample. And (3) putting the impregnated sample into a tube furnace, and carbonizing at 800 ℃ for 2h to obtain a carbonized sample. Grinding the carbonized sample, weighing 0.1g of the carbonized sample, adding a proper amount of water, soaking and stirring, adding a certain amount of mixed solution of nitric acid and sulfuric acid into the suspension, and placing the suspension in an oil bath pan at 140 ℃ for stirring for 7 hours. After the reaction is finished, filtering the solution by using a filter head, and dialyzing the filtrate for 24 hours by using a 1000Da dialysis bag to obtain a light yellow carbon quantum dot aqueous solution. The carbon quantum dot aqueous solution is kept still for more than 3 weeks, no insoluble substances are separated out, and the fluorescence intensity is basically kept unchanged.

And (3) freeze-drying the pig nail derived carbon quantum dot aqueous solution to obtain the pig nail derived carbon quantum dot.

Example 3

Washing, crushing and sieving the bovine nail, and drying in an oven at 60 ℃, wherein the bovine nail powder comprises the following components in percentage by mass: KOH 1: 2 adding a proper amount of water, mixing, and drying at 85 ℃ to obtain an impregnated sample. And (3) putting the impregnated sample into a tube furnace, and carbonizing at 700 ℃ for 2h to obtain a carbonized sample. Grinding the carbonized sample, weighing 0.1g of the carbonized sample, adding a proper amount of water, soaking and stirring, adding a certain amount of hydrogen peroxide solution into the suspension, and placing the suspension in an oil bath kettle at 120 ℃ for stirring for 10 hours. After the reaction is finished, filtering the solution by using a filter head, and dialyzing the filtrate for 24 hours by using a 1000Da dialysis bag to obtain a light yellow carbon quantum dot aqueous solution. The carbon quantum dot aqueous solution is kept still for more than 3 weeks, no insoluble substances are separated out, and the fluorescence intensity is basically kept unchanged.

And (3) freeze-drying the aqueous solution of the bovine-hoof nail derived carbon quantum dots to obtain the bovine-hoof nail derived carbon quantum dots.

Example 4

Washing, crushing and sieving the bovine nail, and drying in an oven at 60 ℃, wherein the bovine nail powder comprises the following components in percentage by mass: k₂CO₃1: 3 adding a proper amount of water, mixing, and drying at 85 ℃ to obtain a dipping sample. And (3) putting the impregnated sample into a tube furnace, and carbonizing at 800 ℃ for 2h to obtain a carbonized sample. Grinding the carbonized sample, weighing 0.1g of the carbonized sample, adding a proper amount of water, soaking and stirring, adding a certain amount of mixed solution of nitric acid and sulfuric acid into the suspension, and placing the suspension in an oil bath pan at 140 ℃ for stirring for 7 hours. After the reaction is finished, filtering the solution by using a filter head, and dialyzing the filtrate by using a 1000Da dialysis bag for 24 hours to obtain a light yellow carbon quantum dot aqueous solution. The carbon quantum dot aqueous solution is kept still for more than 3 weeks, no insoluble substances are separated out, and the fluorescence intensity is basically kept unchanged.

And (3) freeze-drying the aqueous solution of the bovine-hoof nail derived carbon quantum dots to obtain the bovine-hoof nail derived carbon quantum dots.

Example 5

Washing, crushing and sieving the bauhinia, drying in an oven at 60 ℃, and preparing the bauhinia powder according to the mass ratio: KOH 1: 2 adding a proper amount of water, mixing, and drying at 85 ℃ to obtain an impregnated sample. And (3) putting the impregnated sample into a tube furnace, and carbonizing at 700 ℃ for 2h to obtain a carbonized sample. Grinding the carbonized sample, weighing 0.1g of the carbonized sample, adding a proper amount of water, soaking and stirring, adding a certain amount of hydrogen peroxide solution into the suspension, and placing the suspension in an oil bath kettle at 120 ℃ for stirring for 10 hours. After the reaction is finished, filtering the solution by using a filter head, and dialyzing the filtrate by using a 1000Da dialysis bag for 24 hours to obtain a light yellow carbon quantum dot aqueous solution. The carbon quantum dot aqueous solution is kept still for more than 3 weeks, no insoluble substances are separated out, and the fluorescence intensity is basically kept unchanged.

And (3) freeze-drying the water solution of the bauhinia variegates derived carbon quantum dots to obtain the bauhinia variegates derived carbon quantum dots.

Example 6

Washing, crushing and sieving the bauhinia, drying in an oven at 60 ℃, and preparing the bauhinia powder according to the mass ratio: k₂CO₃1: 3 adding a proper amount of water, mixing, and drying at 85 ℃ to obtain a dipping sample. And (3) putting the impregnated sample into a tube furnace, and carbonizing at 800 ℃ for 2h to obtain a carbonized sample. Grinding the carbonized sample, weighing 0.1g of the carbonized sample, adding a proper amount of water, soaking and stirring, adding a certain amount of mixed solution of nitric acid and sulfuric acid into the suspension, and placing the suspension in an oil bath pan at 140 ℃ for stirring for 7 hours. After the reaction is finished, filtering the solution by using a filter head, and dialyzing the filtrate by using a 1000Da dialysis bag for 24 hours to obtain a light yellow carbon quantum dot aqueous solution. The carbon quantum dot aqueous solution is kept still for more than 3 weeks, no insoluble substances are separated out, and the fluorescence intensity is basically kept unchanged.

And (3) freeze-drying the water solution of the bauhinia variegates derived carbon quantum dots to obtain the bauhinia variegates derived carbon quantum dots.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.