CN108275663B - Method for preparing uniform-pore mesoporous boron nitride by melt bubble template method - Google Patents
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Abstract
A method for preparing uniform-pore mesoporous boron nitride by a melt bubble template method comprises the steps of mixing a nitrogen source, a boron source and an auxiliary agent, preserving heat for 0.1-2 hours at 220-500 ℃, then preserving heat for 1-20 minutes at 700 ℃, and forming pores to obtain a precursor; in thatAnd pyrolyzing the mixture of nitrogen and nitrogen at 900-1300 ℃ in the mixture of nitrogen and hydrogen or nitrogen and ammonia to obtain a crude product, washing the crude product in hydrochloric acid, filtering the crude product, and washing the crude product with deionized water and ethanol to obtain porous boron nitride powder. The specific surface area of the product is 150-600 m2The pore diameter is 18-25 nm at most, the technical route is simple, and the preparation method is suitable for mass preparation.
Description
Technical Field
The invention belongs to a preparation technology of porous boron nitride, and particularly relates to a method for preparing mesoporous boron nitride with uniform pore size distribution and high specific surface area by using a nano bubble template in a molten mass.
Background
The porous boron nitride has excellent chemical stability, thermal stability and oxidation resistance. Meanwhile, the catalyst has the characteristics of low density, high porosity and large specific surface area, has great application value in the aspects of sewage treatment, gas adsorption (purification), hydrogen storage, catalyst carriers, non-metal catalysis and the like, and is one of the focuses of researchers at home and abroad in recent years. However, at present, large commercial hexagonal boron nitride is mainly a micron-sized product, the specific surface area is more than 20 square meters per gram, and large specific surface area porous boron nitride is not common.
In recent years, the synthesis of porous boron nitride materials has been reported to have greatly improved in depth and breadth. The following methods are the main methods for preparing these porous boron nitride materials. (1) Pyrolyzing organoborane such as ammonia borane and the like under the atmosphere of protective gas such as nitrogen, argon and the like, and using a chemical foaming method such as the teaching bin and the like to obtain porous boron nitride (adv. Mater. 23 (2011) 4072-4076); (2) the two-stage method represented by Tangchun subject group is used for obtaining microporous boron nitride, and then boric acid and melamine precursors are synthesized, and then pyrolysis is carried out; (3) sofia Marchesini et al, also a typical white graphene synthesis method by calcination of urea, boric acid under inert atmosphere, represents another class of preparation methods for hierarchical porous boron nitride. (micro meso Mater 243 (2017) 154-163). Although the multi-stage porous material has advantages in terms of mass transfer and the like, it is not favorable for specific applications such as selective gas/liquid separation.
Similar to CMK, SBA and other series materials of mesoporous carbon and mesoporous silicon, the mesoporous boron nitride with a regular structure has wide application prospect, but cannot be obtained by a hydrothermal reaction and a liquid crystal soft template method at present, and is not developed greatly. (4) The re-etching of other template materials with single pore diameter to obtain corresponding porous boron nitride is another common preparation strategy, such as using mesoporous carbon and silicon dioxide hard templates (CMK-3, SBA-15), the former can obtain boron nitride with corresponding pore structure by carbon hot replacement, and the latter removes SiO by chemical corrosion after re-etching boron nitride2Thereby obtaining the corresponding mesoporous boron nitride nano material (J. Mater. chem. 15 (2005) 1917-1923).
In summary, the mesoporous boron nitride with relatively regular pores at present has many disadvantages in preparation. The raw material used in the chemical foaming method is expensive ammonia borane, and the specific surface area of the generated porous boron nitride is less than 150m2(ii)/g; the traditional template used by the template method needs to be processed in advance and then removed, so that the process is complex and template residues can be generated. The preparation routes of the porous boron nitride are influenced by organic boron nitrogen sources and hard templates, large commercial boron sources and nitrogen sources are difficult to use, and the preparation routes are difficult to obtain regular mesoporous boron nitride materials (such as more than 10 gram level) in a larger scale, so that research and application exploration of the mesoporous boron nitride in the fields of hydrogen energy storage, carbon dioxide adsorption, oil spill, wastewater and other environmental harm reduction fields are restricted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for efficiently preparing mesoporous boron nitride with relatively regular pore diameter in a large scale.
The method uses the most conventional bulk chemical boron source and nitrogen source, and has the core that the molten salt technology and the bubble template technology are combined to separate the precursor obtained by pore forming and the high-temperature calcination nitridation, so that the method has the characteristics of simplicity, convenience, high efficiency and low cost.
The method is realized by the following technical scheme:
(1) a first stage: calcining at low temperature to form pores to obtain precursor, wherein urea is molten during calcining, and boric acid and urea form (BO)x(BN)yThe precursor is slowly decomposed by the boron source and the nitrogen source, nano bubbles are generated in situ and serve as a template, when the gas production raw material is exhausted, a porous structure of the precursor is obtained, and special gas protection is not needed in the calcination at the stage.
Specifically, mixing a nitrogen source, a boron source and an auxiliary agent according to a mass ratio of 3-8: 1: 0.001-0.05, preserving heat for 0.1-2 hours at 220-500 ℃, then preserving heat for 1-20 minutes at 700 ℃, and performing pore-forming to obtain a precursor;
the nitrogen source is urea or a mixture of urea and melamine or ammonium carbonate, wherein the melamine or ammonium carbonate is present in the mixture in an amount of less than 10 wt.%.
The boron source is boric acid, or a mixture of boric acid and boron oxide, wherein the weight ratio of boric acid to boron oxide is 1: 8-10.
The purpose of adding a small amount of auxiliary agent is to regulate the viscosity of the melt, influence the size of nano bubbles and regulate the surface chemical environment, the crystallization degree and the specific surface area of the product, and the auxiliary agent is one of nitrate and chloride of iron, cobalt, nickel and lanthanum elements and sodium carbonate and borax.
(2) And (3) pyrolyzing the calcination precursor in the second stage to obtain a crude product:
pyrolyzing the precursor in nitrogen, a nitrogen-hydrogen mixed gas or a nitrogen-ammonia mixed gas at 900-1300 ℃ to obtain a crude product, wherein the nitrogen-hydrogen mixed gas is the nitrogen-hydrogen mixed gas with the hydrogen concentration of 2-5 wt.%, and the nitrogen-ammonia mixed gas is the nitrogen-ammonia mixed gas with the ammonia concentration of 2-20 wt.%.
(3) And (3) purifying a crude product:
and (3) washing the crude product in 0.1-3 mol/L hydrochloric acid, filtering the product, and washing with deionized water and ethanol to obtain porous boron nitride powder, wherein the acid washing temperature is 20-60 ℃.
The method for synthesizing the mesoporous boron nitride has the advantages that:
1. the used reagent is cheap and easy to obtain, and the residual by-product is less and easy to purify;
2. the used technical route is simple, the technical difficulty is small, and the method is suitable for mass preparation;
3. the specific surface area of the obtained product is 150-600 m2The/g is adjustable;
4. the pore size of the obtained product is 18-25 nm at most.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of a product prepared by using example 1 of the present invention.
FIG. 2 is a Transmission Electron Microscope (TEM) of the product prepared by example 1 of the present invention.
FIG. 3 is an adsorption desorption/adsorption equipartition curve of the product prepared in example 1 of the present invention.
FIG. 4 is a graph of pore size distribution of a product prepared using example 1 of the present invention.
FIG. 5 is a transmission electron micrograph of a large area of the product obtained in example 3 of the present invention.
FIG. 6 is a transmission electron micrograph of a product obtained in example 4 of the present invention.
FIG. 7 is a transmission electron micrograph of a product obtained in example 5 of the present invention.
FIG. 8 is a transmission electron micrograph of a product obtained in example 5 of the present invention.
Detailed Description
Example 1:
100 g of boric acid, 400 g of urea and 1 g of ferric nitrate are uniformly mixed, heated to 300 ℃ at the heating rate of 10 ℃/min in an electric furnace and kept for 20 minutes to obtain a precursor, and then the precursor is cured for 1 minute at 700 ℃. Putting the precursor into a graphite boat nitrogen-hydrogen mixed gas (5 wt% H)2/N2) Under the protection of atmosphere, the temperature is raised to 1000 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 2 hours to obtain a crude product. The crude product was then placed in 500 ml of 0.5 mol/L hydrochloric acid and stirred at 60 ℃ for 2 hours. The product was filtered and washed with deionized water and ethanol and dried for 12 hours. 40 g of product are obtained.
FIG. 1 shows that the obtained product is pure boron nitride, FIG. 2 is a transmission electron micrograph of the obtained product, it can be seen that the product has porous characteristics and relatively uniform pore diameter, the average size is about 18 nm, and FIG. 3 is an isothermal adsorption and desorption curve, P/P, of the obtained mesoporous boron nitride in 77K nitrogen gas0= 0.45 has a typical jump in mesoporous structure, and the specific surface area of the sample is calculated by using the BET equationProduct of 281m2(ii) in terms of/g. The pore size distribution obtained by the BJH method using the desorption branch is shown in FIG. 4. As can be seen from the combination of FIG. 2 and FIG. 4, the most probable pore diameter is 18 nm, and the pore size is mainly between 10 nm and 40 nm.
Example 2:
100 g of boric acid, 270 g of urea, 30 g of ammonium carbonate and 2 g of cobalt nitrate are uniformly mixed, heated to 220 ℃ at the heating rate of 10 ℃/min in an electric furnace and kept for 2 hours to obtain a precursor, and then the precursor is cured for 10 minutes at 700 ℃. Putting the precursor into a graphite boat nitrogen-hydrogen mixed gas (2 wt.% H)2/N2) Under the protection of atmosphere, the temperature is raised to 1000 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 2 hours to obtain a crude product. The crude product is subsequently stirred in 500 ml of 3mol/L hydrochloric acid at 40 ℃ for 4 hours. Filtering the product, washing with deionized water and ethanol, drying, and measuring the specific surface area of the sample to be 220 m2The largest pore diameter is 25 nm, and the pore size is mainly between 8 and 50 nm.
Example 3:
10 g of boric acid, 90 g of boron oxide powder, 800 g of urea and 5 g of ferric nitrate are uniformly mixed, heated to 500 ℃ at the heating rate of 10 ℃/min in an electric furnace and insulated for 6 minutes, and then cured for 20 minutes at 700 ℃. Putting the precursor into a graphite boat nitrogen-hydrogen mixed gas (20 wt.% NH)3/N2) Under the protection of atmosphere, the temperature is raised to 900 ℃ at the heating rate of 10 ℃/min, and the temperature is preserved for 3 hours to obtain a crude product. The crude product is subsequently stirred in 500 ml of 1 mol/L hydrochloric acid at 50 ℃ for 4 hours. Filtering the product, washing with deionized water and ethanol, and drying for 12 hr to obtain product with specific surface area of 150m2The transmission electron micrograph is shown in FIG. 5. The most probable pore diameter is 23 nm, and the pore size is mainly between 8 and 50 nm.
Example 4:
100 g of boric acid, 400 g of urea and 0.1 g of sodium carbonate are uniformly mixed, heated to 300 ℃ at the heating rate of 10 ℃/min in an electric furnace and kept for 20 minutes to obtain a precursor, and then the precursor is cured for 1 minute at 700 ℃. And putting the precursor into a graphite boat under the protection of nitrogen atmosphere, heating to 900 ℃ at the heating rate of 10 ℃/min, and preserving the temperature for 30 minutes to obtain a crude product. The crude product is subsequently treated with 0.1 mol/L hydrochloric acidStirred at 20 ℃ for 10 minutes. Filtering the product, washing with deionized water and ethanol, and drying to obtain product with specific surface area of 600m2The most probable pore diameter is 23 nm, and the size of the pores is mainly between 8 and 50nm as shown in a transmission electron micrograph of figure 6.
Example 5:
100 g of boric acid, 395 g of urea, 5 g of melamine and 0.5 g of nickel nitrate are uniformly mixed, heated to 300 ℃ at the heating rate of 10 ℃/min in an electric furnace and kept for 20 minutes to obtain a precursor, and then the precursor is solidified at 700 ℃. Putting the precursor into a graphite boat with 10wt.% NH3-N2Under the protection of mixed gas of nitrogen and hydrogen, the temperature is raised to 950 ℃ at the heating rate of 10 ℃/min, and the temperature is preserved for 1 hour to obtain a crude product. The crude product was then stirred in 2 mol/L hydrochloric acid at 60 ℃ for 2 hours. The product is filtered, washed by deionized water and ethanol, dried for 12 hours, and the specific surface area of the sample is 300 m2The most probable pore diameter is 23 nm, the pore size is mainly between 10 and 45nm, and a corresponding transmission electron micrograph is shown in figure 7.
Example 6:
100 g of boric acid, 400 g of urea and 0.1 g of ferric chloride are uniformly mixed, heated to 300 ℃ at the heating rate of 10 ℃/min in an electric furnace and kept for 20 minutes to obtain a precursor, and then the precursor is cured for 1 minute at 700 ℃. Putting the precursor into a graphite boat N2Under the protection of atmosphere, heating to 1300 ℃ at the heating rate of 10 ℃/min, and preserving the temperature for 20 minutes to obtain a crude product. The crude product was subsequently treated with 2 mol/L hydrochloric acid at 40 ℃ for 10 minutes. Filtering the product, washing with deionized water and ethanol, and drying to obtain product with specific surface area of 230 m2The most probable pore diameter is 22 nm, and the corresponding transmission electron micrograph of the pore size is mainly between 8 and 45nm, which is shown in figure 8.
Claims (5)
1. A method for preparing uniform-pore mesoporous boron nitride by a melt bubble template method is characterized by comprising the following steps: mixing a nitrogen source, a boron source and an auxiliary agent according to a mass ratio of 3-8: 1: 0.001-0.05, preserving heat for 0.1-2 hours at 220-500 ℃, then preserving heat for 1-20 minutes at 700 ℃, and performing pore-forming to obtain a precursor; the nitrogen source is urea or a mixture of urea and melamine or ammonium carbonate; the boron source is boric acid or a mixture of boric acid and boron oxide; the auxiliary agent is nitrate or chloride of iron, cobalt, nickel and lanthanum; or one of sodium carbonate and borax; (2) pyrolyzing the precursor in nitrogen, nitrogen-hydrogen mixed gas or nitrogen-ammonia mixed gas at 900-1300 ℃ to obtain a crude product; and (3) washing the crude product in 0.1-3 mol/L hydrochloric acid, filtering the product, and washing with deionized water and ethanol to obtain porous boron nitride powder, wherein the acid washing temperature is 20-60 ℃.
2. The method for preparing the uniform-pore mesoporous boron nitride by the melt bubble template method according to claim 1, wherein the method comprises the following steps: the melamine or ammonium carbonate content in the mixture is less than 10 wt%.
3. The method for preparing the uniform-pore mesoporous boron nitride by the melt bubble template method according to claim 1, wherein the method comprises the following steps: the weight ratio of boric acid to boron oxide in the boric acid and boron oxide mixture is 1: 8-10.
4. The method for preparing the uniform-pore mesoporous boron nitride by the melt bubble template method according to claim 1, wherein the method comprises the following steps: the nitrogen-hydrogen mixed gas is a nitrogen-hydrogen mixed gas with the hydrogen concentration of 2-5 wt%.
5. The method for preparing the uniform-pore mesoporous boron nitride by the melt bubble template method according to claim 1, wherein the method comprises the following steps: the nitrogen-ammonia mixed gas is a nitrogen-ammonia mixed gas with the ammonia gas concentration of 2-20 wt%.
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| JP7349921B2 (en) * | 2020-01-24 | 2023-09-25 | デンカ株式会社 | Hexagonal boron nitride sintered body |
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