CN112551507B - Heteroatom-doped starch carbon and preparation method thereof - Google Patents
Heteroatom-doped starch carbon and preparation method thereof Download PDFInfo
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Abstract
The invention discloses heteroatom doped starch carbon and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Drying the modified starch containing the heteroatom, adding the dried modified starch into an organic acid solution, uniformly mixing, standing and drying to obtain a heteroatom-doped starch carbon precursor; the modified starch is as follows: one or more of cationic starch, anionic starch and amphoteric starch; (2) Heating the heteroatom-doped starch carbon precursor to 400-1000 ℃ at the speed of 1-10 ℃/min under the protection of inert atmosphere, and roasting at constant temperature for 0.5-5h to obtain the heteroatom-doped starch carbon. The preparation method is simple and easy to operate, not only greatly reduces the production cost, but also solves the problems of low yield and small doping amount of the prior heteroatom-doped carbon material.
Description
Technical Field
The invention relates to the technical field of porous carbon materials, in particular to heteroatom-doped starch carbon and a preparation method thereof.
Background
The porous carbon material has the advantages of acid and alkali corrosion resistance, low price and the like as a material with high specific surface area and developed pores, and is widely applied to the fields of adsorption, decoloration, refining, separation, catalysis and the like. Currently, the most widely used porous carbon material is activated carbon material. However, the pore structure of the activated carbon material is complex and the majority of the activated carbon material is micropores with a diameter of less than 2 nanometers, and in addition, the impurity content of the activated carbon is high, which limits the application of the activated carbon in high-end fields such as catalysis and analysis.
After the heteroatom is introduced into the porous carbon skeleton, the electronegativity of the introduced heteroatom is different from that of a carbon atom, so that the surface property of the carbon material can be effectively changed, brand new properties such as surface acid-base regulation, surface electronic arrangement regulation, micro-region structure regulation and the like are endowed, and the heteroatom plays a prominent role in the fields of electrochemistry, catalysis, environmental chemistry and the like. At present, more preparation methods of heteroatom-doped carbon materials are reported, but most of the reported preparation methods are that expensive chemical reagents are used for carrying out post-modification treatment on the carbon materials, and the carbon materials produced by the method not only have the problem of low heteroatom doping amount, but also are difficult to directionally regulate and control the content and the type of the required heteroatom doping, and simultaneously bring about the problem of a large amount of waste acid and waste water. In addition, the complicated preparation steps, expensive heteroatom-containing reagents and low yield of carbon materials are all problems which limit the large-scale production and application of heteroatom-doped carbon materials. Therefore, a preparation method for preparing the heteroatom-doped carbon material with low cost and high efficiency needs to be found.
The starch is used as a renewable material, has rich content, simple and easily obtained raw materials and low preparation cost, and can be used for preparing pure carbon materials without impurities through high-temperature carbonization. For example, patent CN107115883B proposes a method for preparing nitrogen-doped mesoporous carbon material by using natural starch as raw material, and patent CN107043109A proposes a method for preparing super-capacitor carbon by using starch. However, the above-mentioned prior patents have problems that the amount of nitrogen atom doped and the species are difficult to control, which often depends on the protein content in starch, and the bio-protein content of starch raw materials of different types and different production places are largely different, which makes quantitative control difficult. In addition, the starch charcoal produced by the sol-gel method as reported in patents US2014288297A1, US9457338B2, etc. has a long technical route and causes a great amount of water resource waste and the following problems of wastewater treatment. Therefore, there is an urgent need to develop new methods for more efficiently preparing heteroatom-doped starch carbons.
Disclosure of Invention
The invention provides a method for preparing heteroatom-doped starch carbon by taking modified starch as a raw material, which is simple and easy to operate, not only greatly reduces the production cost, but also solves the problems of low yield and low doping amount of the existing heteroatom-doped carbon material.
The specific technical scheme of the invention is as follows:
a preparation method of heteroatom doped starch carbon comprises the following steps:
(1) Drying the modified starch containing the heteroatom, adding the modified starch into an organic acid solution, uniformly mixing, standing and drying to obtain a heteroatom-doped starch carbon precursor;
the modified starch comprises: one or more of cationic starch, anionic starch and amphoteric starch;
(2) Heating the heteroatom-doped starch carbon precursor to 400-1000 ℃ at the speed of 1-10 ℃/min under the protection of inert atmosphere, and roasting at constant temperature for 0.5-5h to obtain the heteroatom-doped starch carbon.
The preparation method of the invention uses the modified starch containing heteroatom as a precursor, and prepares the heteroatom-doped starch carbon in situ by directly carbonizing the modified starch.
The modified starch can be a commercial product or a self-made product.
Preferably, the preparation method of the modified starch comprises the following steps:
(i) Adding a heteroatom reagent and an alkali solution into the dried starch raw material, and heating, stirring and reacting;
(ii) And (3) cooling to room temperature after the reaction is finished, adding acid liquor, adjusting the pH value of the reaction mixed liquor to 6.5-7.5, filtering, and drying filter residues to obtain the modified starch.
The starch raw material is rich in hydroxyl functional groups, and the invention combines starch and heteroatom reagent through chemical reaction under certain conditions and then carbonizes to prepare the heteroatom-doped starch carbon material. A plurality of heteroatom-doped starch carbons can be effectively prepared by selectively increasing or decreasing the adding types and adding sequences of heteroatom reagents, heteroatoms grafted with glucose units in starch can be better retained in a prepared carbon material framework in a high-temperature roasting process, and the results of elemental analysis and ICP show that the heteroatoms can be effectively and uniformly doped in a carbon material structure.
In the step (i), the starch raw material is one or more of sweet potato starch, cassava starch, mung bean starch, potato starch, wheat starch and corn starch which are mixed in any proportion.
In the step (i), the heteroatom reagent is one or more of boric acid, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, melamine, dicyandiamide, urea, phosphoric acid, sodium monohydrogen phosphate, sodium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, thiourea and passivated sulfuric acid; all of the required heteroatom reagents are added in one step as required or sequentially in the order required.
In the step (i), the mass ratio of the starch raw material to the heteroatom reagent is 1:0.01-10.
In the step (i), the alkali solution is one or more of a sodium hydroxide solution, ammonia water, a sodium bicarbonate solution, a sodium carbonate solution, a potassium bicarbonate solution, a potassium carbonate solution, an ammonia bicarbonate solution and an ammonia carbonate solution.
Further, the mass fraction of the alkali solution is 1-20%; the mass ratio of the starch raw material to the alkali solution is 1.
In the step (1), in the organic acid solution, the organic acid is one or more of formic acid, acetic acid, oxalic acid, citric acid, malic acid, tartaric acid, tannic acid, sulfonic acid and sulfinic acid; the mass ratio of the modified starch to the organic acid is 1.
In the step (1), in the organic acid solution, a solvent is one or more of deionized water, methanol, absolute ethyl alcohol, acetone and glycerol; the mass ratio of the modified starch to the solvent is 1.1-10.
In the step (2), the inert atmosphere is one or more of nitrogen, argon and helium; the flow rate is 10-1000mL/min.
Preferably, in the step (2), the temperature is raised to 400-900 ℃, and the mixture is roasted for 1-5h at constant temperature.
The invention also provides the heteroatom doped starch carbon prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method takes the modified starch as a raw material, wherein the heteroatom functional group chemically connected with starch molecules is a heteroatom source, realizes the one-step in-situ synthesis of the heteroatom-doped starch carbon under the condition of no need of expensive reagents and complex operation conditions, has mild condition and simple operation, can obtain the starch carbon material with high added value in one step, and can realize large-scale production;
(2) The preparation method of the invention utilizes the characteristic that starch has rich hydroxyl groups to chelate the heteroatom reagent with the glucose unit of the starch under the action of the catalyst, so that the heteroatom can be better reserved in the high-temperature roasting process, and compared with the method for generating gaseous molecules (NH) by utilizing the heteroatom pyrolysis reported in the prior patent and literature 3 、H 2 S, etc.) and then gas-solid reaction to obtain the heteroatom doped carbon material, the invention has outstanding advantages in the aspect of heteroatom retention and reduces the production cost;
(3) The preparation method of the invention greatly expands the application field (paper making, textile and the like) of the traditional modified starch by utilizing the modified starch to prepare the high-end carbon material, improves the international competitiveness of the carbon material in China at present, and realizes the purposes of expansion of the application of the carbon material and resource utilization, thereby being a green process.
Detailed Description
Example 1
Drying potato starch in a 100 ℃ oven for 3h, dissolving 1g of boric acid in 50ml of deionized water, uniformly stirring, adding 10g of dried potato starch into the solution, adding 0.1g of a 10% sodium hydroxide solution by mass fraction, stirring in a 80 ℃ water bath for 2h at the rotating speed of 100 r/min, adding a certain amount of 5% dilute hydrochloric acid after complete reaction to adjust the pH value of the solution to 7.0, filtering the starch, placing in the oven, and drying at 110 ℃ for 2h. Uniformly mixing the prepared modified starch with 10mL of aqueous solution containing 1g of acetic acid, standing at 20 ℃ for 8h, drying in an oven at 150 ℃ for 10h, carbonizing at 800 ℃ for 2h in a tubular furnace under nitrogen atmosphere at the nitrogen flow of 30mL/min, and taking out a sample to obtain the boron-doped starch carbon.
Example 2
Placing potato starch in an oven at 90 ℃ for drying for 12h, dissolving 1g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in 20ml of deionized water, uniformly stirring, adding 10g of dried potato starch into the solution, adding 0.05g of 10% sodium hydroxide solution by mass fraction, stirring in a water bath at 100 ℃ for 5h at the rotating speed of 200 r/min, after complete reaction, adding a certain amount of 3% diluted acetic acid to adjust the pH value of the solution to 7.0, filtering the starch, placing in the oven, and drying at 120 ℃ for 10h. Uniformly mixing the prepared modified starch with 20mL of aqueous solution containing 2g of p-toluenesulfonic acid, standing at 20 ℃ for 8h, drying in an oven at 150 ℃ for 10h, carbonizing at 600 ℃ for 2h in a tubular furnace under nitrogen atmosphere, wherein the nitrogen flow is 30mL/min, and taking out a sample to obtain the nitrogen-doped starch carbon.
Example 3
Placing corn starch in an oven at 120 ℃ for drying for 24 hours, dissolving 2g of concentrated phosphoric acid and 0.5g of urea in 60ml of deionized water, uniformly stirring, adding 10g of dried corn starch into the solution, adding 0.2g of sodium hydroxide solution with the mass fraction of 10%, stirring in a water bath at 100 ℃ for 6 hours at the rotating speed of 60 r/min, adding a certain amount of dilute hydrochloric acid with the mass fraction of 1% after complete reaction to adjust the pH value of the solution to 6.5, filtering the starch, placing in the oven, and drying at 120 ℃ for 12 hours. Uniformly mixing the prepared modified starch with 5mL of ethanol solution containing 1g of tartaric acid, standing at 20 ℃ for 8h, drying in an oven at 150 ℃ for 10h, carbonizing at 900 ℃ for 2h in a tubular furnace under nitrogen atmosphere with the nitrogen flow of 30mL/min, and taking out a sample to obtain the nitrogen-phosphorus double-doped starch carbon.
Example 4
Drying the cassava starch in a 120 ℃ oven for 24 hours, dissolving 1g of ammonium monohydrogen phosphate and 1g of inerted sulfuric acid in 80ml of deionized water, uniformly stirring, adding 10g of dried cassava starch into the solution, adding 0.1g of 10% sodium bicarbonate solution, stirring in a 100 ℃ oil bath for 5 hours at a rotation speed of 500 r/min, adding a certain amount of 1% diluted hydrochloric acid after complete reaction to adjust the pH value of the solution to 6.5, filtering the starch, placing the starch in the oven, and drying at 110 ℃ for 20 hours. Uniformly mixing the prepared modified starch with 2mL of glycerin solution containing 1g of tannic acid, standing at 20 ℃ for 8h, drying in an oven at 150 ℃ for 10h, carbonizing at 1000 ℃ for 2h in a tubular furnace under the nitrogen atmosphere, wherein the nitrogen flow is 30mL/min, and taking out a sample to obtain the phosphorus-sulfur double-doped starch carbon.
Example 5
Drying potato starch in a 90 ℃ oven for 13h, dissolving 1g of ammonium dihydrogen phosphate and 1g of thiourea in 70ml of deionized water, uniformly stirring, adding 10g of dried potato starch into the solution, adding 0.1g of 10% sodium hydroxide solution by mass, stirring in a 80 ℃ water bath for 2h at the rotating speed of 100 r/min, adding a certain amount of 5% dilute hydrochloric acid after complete reaction to adjust the pH value of the solution to 7.0, filtering the starch, placing in the oven, and drying at 110 ℃ for 2h. Uniformly mixing the prepared modified starch with 10mL of acetone solution containing 1g of formic acid, standing at 20 ℃ for 8h, drying in an oven at 150 ℃ for 10h, carbonizing at 700 ℃ for 1h in a tubular furnace under nitrogen atmosphere, wherein the nitrogen flow is 30mL/min, and taking out a sample to obtain the nitrogen-phosphorus-sulfur tri-doped starch carbon.
Example 6
Placing potato starch in a 100 ℃ oven for drying for 3h, dissolving 1g of sodium monohydrogen phosphate in 50ml of deionized water, uniformly stirring, adding 10g of dried potato starch into the solution, adding 0.1g of sodium hydroxide solution with the mass fraction of 3%, stirring in a 80 ℃ water bath for 2h at the rotating speed of 100 r/min, adding a certain amount of dilute hydrochloric acid with the mass fraction of 5% after complete reaction to adjust the pH value of the solution to 7.0, filtering the starch, placing in the oven, and drying at 110 ℃ for 2h. Adding 80mL of deionized water solution containing 1.2g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the prepared phosphorus modified starch, adding 0.1g of sodium bicarbonate solution with the mass fraction of 3%, stirring in a water bath at 90 ℃ for 4 hours at the rotating speed of 400 r/min, adding a certain amount of dilute acetic acid with the mass fraction of 5% after complete reaction to adjust the pH value of the solution to 6.5, filtering the starch, placing the starch in an oven, and drying at 120 ℃ for 1.5 hours. Uniformly mixing the prepared modified starch with 30mL of aqueous solution containing 2g of formic acid, standing at 20 ℃ for 8h, drying in an oven at 150 ℃ for 10h, carbonizing at 800 ℃ for 4h in a tube furnace under helium atmosphere with the flow of 50mL/min, and taking out a sample, namely the nitrogen-phosphorus double-doped starch carbon.
Comparative example 1
Placing potato starch in a 100 ℃ oven for drying for 3h, taking 1g boric acid and 10g dried potato starch to be uniformly mixed, carbonizing the mixture in a tube furnace at 800 ℃ for 2h under nitrogen atmosphere with the nitrogen flow of 30mL/min, and taking out a sample to obtain boron-doped starch carbon.
Comparative example 2
Drying corn starch in a 120 ℃ oven for 24h, taking 0.5g and 10g of dried corn starch solid phase, uniformly mixing, carbonizing the mixture in a tube furnace at 900 ℃ for 2h under nitrogen atmosphere with the nitrogen flow of 30mL/min, and taking out a sample to obtain the nitrogen-doped starch carbon.
Physical properties of the heteroatom-doped starch carbons prepared in examples 1 to 6 and comparative examples 1 and 2 are shown in table 1 below, and it can be seen from table 1 that the heteroatom-doped starch carbons prepared in examples 1 to 6 all have large specific surface areas; the doped heteroatoms in the raw materials can effectively enter a material framework after high-temperature roasting. It can be seen by comparing example 1 with comparative example 1, and example 3 with comparative example 2 that the heteroatom doped starch carbon prepared by the method of the present invention has obvious advantages in terms of heteroatom doping amount, specific surface area and pore volume.
TABLE 1
The technical solutions and advantages of the present invention have been described in detail with reference to the above embodiments, it should be understood that the above embodiments are only specific examples of the present invention and should not be construed as limiting the present invention, and any modifications, additions, equivalents and the like made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of heteroatom doped starch carbon is characterized by comprising the following steps:
(1) Drying the modified starch containing the heteroatom, adding the dried modified starch into an organic acid solution, uniformly mixing, standing and drying to obtain a heteroatom-doped starch carbon precursor;
the modified starch is as follows: one or more of cationic starch, anionic starch and amphoteric starch; the preparation method of the modified starch comprises the following steps:
(i) Adding a heteroatom reagent and an alkali solution into a dried starch raw material, and heating, stirring and reacting; the mass ratio of the starch raw material to the heteroatom reagent is 1;
the heteroatom reagent is one or more of boric acid, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, melamine, dicyandiamide, urea, phosphoric acid, sodium monohydrogen phosphate, sodium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, thiourea and passivated sulfuric acid; adding all the required heteroatom reagents according to the required step or sequentially adding the required heteroatom reagents according to the sequence;
the alkali solution is one or more of sodium hydroxide solution, ammonia water, sodium bicarbonate solution, sodium carbonate solution, potassium bicarbonate solution, potassium carbonate solution, ammonium bicarbonate solution and ammonium carbonate solution;
(ii) Cooling to room temperature after the reaction is finished, adding acid liquor, adjusting the pH value of the reaction mixed liquor to 6.5-7.5, filtering, and drying filter residues to obtain the modified starch;
(2) Heating the heteroatom-doped starch carbon precursor to 400-1000 ℃ at the speed of 1-10 ℃/min under the protection of inert atmosphere, and roasting at constant temperature for 0.5-5h to obtain the heteroatom-doped starch carbon.
2. The method for preparing heteroatom-doped starch charcoal as claimed in claim 1, wherein in step (i), the starch material is one or more of sweet potato starch, tapioca starch, mung bean starch, potato starch, wheat starch and corn starch in any proportion.
3. The method for preparing heteroatom-doped starch carbon as claimed in claim 1, wherein the mass fraction of the alkali solution is 1-20%; the mass ratio of the starch raw material to the alkali solution is 1.
4. The method for preparing heteroatom-doped starch charcoal according to claim 1, wherein in the step (1), the organic acid in the organic acid solution is one or more of formic acid, acetic acid, oxalic acid, citric acid, malic acid, tartaric acid, tannic acid, sulfonic acid and sulfinic acid; the mass ratio of the modified starch to the organic acid is 1.
5. The method for preparing heteroatom-doped starch carbon as claimed in claim 1, wherein in the organic acid solution, the solvent is one or more of deionized water, methanol, absolute ethyl alcohol, acetone and glycerol; the mass ratio of the modified starch to the solvent is 1.
6. The method for preparing heteroatom-doped starch carbon according to claim 1, wherein in the step (2), the temperature is raised to 400-900 ℃, and the mixture is roasted at a constant temperature for 1-5h.
7. A heteroatom-doped starch char produced by the production method according to any one of claims 1 to 6.
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