CN108441986B - Macroporous boron nitride fiber and preparation method thereof - Google Patents
Macroporous boron nitride fiber and preparation method thereof Download PDFInfo
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- CN108441986B CN108441986B CN201810184213.2A CN201810184213A CN108441986B CN 108441986 B CN108441986 B CN 108441986B CN 201810184213 A CN201810184213 A CN 201810184213A CN 108441986 B CN108441986 B CN 108441986B
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Abstract
A macroporous boron nitride fiber is prepared by using retinervus Luffae fructus as carbon source template, and replacing carbon element in retinervus Luffae fructus with boron source and nitrogen source to obtain macroporous boron nitride fiber with same pore structure as original retinervus Luffae fructus matrix. The preparation method comprises the following steps: cleaning and drying the loofah sponge, putting a boron source and the loofah sponge into a double-layer crucible according to a ratio, putting the boron source into the lower layer of the double-layer crucible, putting the loofah sponge into the upper layer of the double-layer crucible, putting the double-layer crucible into a high-temperature furnace, introducing a nitrogen source, raising the temperature to 1300 ℃ and 1600 ℃, keeping the temperature for a period of time, and cooling to room temperature to obtain the white loofah sponge skeleton-shaped boron nitride fiber. The invention adopts a replacement mode to replace carbon element in the loofah sponge with boron nitride, not only has the physical and chemical properties of the boron nitride, but also can obtain the same pore structure as the original loofah sponge matrix, has large specific surface area and uniform pores, has stronger adsorption performance on heavy metal, dye and oil stain, and has good application prospect in the field of wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a boron nitride fiber used in a wastewater treatment process and a preparation method thereof.
Background
Boron nitride is a synthetic compound consisting of boron (B) which is an element of the third group (III) and nitrogen (N) which is an element of the fifth group (V), and has a structure similar to that of graphite, and is called white graphite. Boron nitride has excellent physical and chemical properties, and has been widely noticed by researchers. At present, researchers have achieved a great deal of successful research results in the preparation of boron nitride materials, and a series of boron nitride materials with different structures, such as nanotubes, nanowires, nanorods, nanosheets, nanobelts, nanospheres, porous fibers and the like, are successfully prepared. In recent years, with the synthesis of porous boron nitride materials with large specific surface areas, researchers find that porous boron nitride materials with large specific surface areas have wide application prospects in the aspect of solving the environmental pollution, and can be applied to the field of sewage treatment. Compared with the traditional activated carbon adsorption material, the porous boron nitride material has more advantages when being used as an adsorbent. The boron nitride material contains B-N bonds and C-C bonds which are isoelectrons, so the crystal structure is similar to that of graphite, but the physical and chemical properties are obviously different from those of the graphite material. The boron nitride material has good insulativity, high-temperature chemical inertness and thermal stability. In addition, B — N has a local polarity that is not possessed by the C — C bond, and when used as an adsorbent, the polar site generally improves the adsorption property, so boron nitride materials are theoretically promising high-efficiency catalytic adsorbents that can be stably used at high temperatures or under extreme conditions. In addition, since boron nitride can be used in air or organic atmosphere at a high temperature of 800 ℃ or higher, the regeneration process after adsorption is relatively easy and safe.
At present, the research on the preparation of porous boron nitride materials and the use of the porous boron nitride materials as adsorbents at home and abroad has been greatly developed and advanced, and when the boron nitride materials are used as the adsorbents, the porous boron nitride materials have large specific surface area, developed pore structures, super-strong adsorption capacity, good reproducibility and safety, and are the adsorbent materials with the most application prospect at present. However, in the research of the preparation of the porous boron nitride material, there are some problems, such as how to correctly select a hard template which meets the particle size, morphology and surface characteristics of the target material when the hard template is used for preparing the porous boron nitride material; the template may have the phenomena of agglomeration, etching and the like in the process of being coated by the target material; the process of removing the template may result in collapse, breakage of the shell of the target material and incomplete removal often is accompanied by a certain amount of residue that is detrimental to achieving the high purity requirements of the target material. In addition, harmful byproducts are generated in the process of removing the hard template by using extremely dangerous acid-base solution (such as HF, NaOH and the like), and the method is environment-friendly. In addition, the research on the performance and application of porous boron nitride materials still needs to be further advanced. Therefore, a more reasonable raw material is found to prepare the porous boron nitride adsorbing material, so that the potential of the porous boron nitride adsorbing material in the aspect of environmental sewage treatment is improved, and the porous boron nitride adsorbing material is a target jointly pursued by many scientific researchers and industrial people.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and firstly provides a macroporous boron nitride fiber which has very simple preparation process, low cost and easy obtainment.
The macroporous boron nitride fiber provided by the invention is prepared by using loofah sponge as a carbon source template and replacing carbon elements in the loofah sponge by a boron source and a nitrogen source, so that the macroporous boron nitride fiber with the same pore structure as the original loofah sponge matrix is obtained.
According to the invention, the natural plant loofah sponge is used as a carbon source template, and the replacement mode is adopted to replace carbon elements in the loofah sponge, so that the physical and chemical properties of the boron nitride can be achieved, the pore structure which is the same as that of the original loofah sponge matrix can be obtained, the loofah sponge has a large specific surface area, and has an ultrahigh adsorption capacity and surface activity, and has a rapid and efficient adsorption capacity for heavy metal ions, dyes, toxic gases and organic pollutants in the environment, and also has strong thermal stability, chemical stability and oxidation resistance. Furthermore, the macroporous boron nitride fiber is prepared by taking the waste loofah sponge as a raw material, is cheap and easy to obtain, has very low cost and light weight, does not need to process the raw material, has higher yield of products, and is relatively easy and safe in the regeneration process of the adsorbed material.
The invention also provides a preparation method of the macroporous boron nitride fiber, which comprises the following steps:
cleaning retinervus Luffae fructus with water and ethanol respectively, and drying;
weighing a boron source and dried loofah sponge according to a ratio, and then respectively placing the boron source and the loofah sponge in a double-layer crucible, wherein the boron source is placed at the lower layer of the double-layer crucible, the loofah sponge is placed at the upper layer of the double-layer crucible, and then the double-layer crucible is placed in a high-temperature furnace;
introducing a nitrogen source into the high-temperature furnace, raising the temperature to 1300-1600 ℃, keeping the temperature for a period of time, and naturally cooling to room temperature to obtain the white loofah skeleton-shaped white boron nitride fiber.
In the preparation step of the macroporous boron nitride fiber, the boron source is boron nitride; the nitrogen source is N2。
In the preparation steps of the macroporous boron nitride fiber, the loofah sponge can be alternately cleaned by water and ethanol for a plurality of times by ultrasonic waves, and then dried for 20-30h at the temperature of 70-100 ℃.
In the preparation step of the macroporous boron nitride fiber, the boron source and the loofah sponge small pieces are weighed according to the ratio of 2-4: 1.
In the preparation step of the macroporous boron nitride fiber, the flow rate of the nitrogen source introduced into the high-temperature furnace is 300-500 sccm.
In the preparation step of the macroporous boron nitride fiber, the temperature of the nitrogen source introduced into the high-temperature furnace is increased from room temperature to 1300-1600 ℃ at the heating rate of 5 ℃/min.
In the preparation step of the macroporous boron nitride fiber, the nitrogen source introduced into the high-temperature furnace is heated to 1300-1600 ℃, then the flow rate of the nitrogen source is increased to 1200-1600sccm, the temperature is kept for 5-6h, and then the temperature is naturally reduced to the room temperature.
Compared with the existing carbonization covering treatment mode, the macroporous boron nitride fiber prepared by adopting the carbon replacement mode has the advantages of very simple preparation process steps, low cost, easiness in realization and small environmental pollution, and the specific surface area of the product can be adjusted by adjusting the temperature condition of the reaction, so that the obtained product has a very large pore structure, can fully and effectively degrade organic pollutants, is suitable for industrial production and has good application prospect in the field of wastewater treatment.
Drawings
FIG. 1 is a photograph of a macroporous boron nitride fiber prepared in accordance with an embodiment of the present invention;
FIG. 2 is an XRD pattern of a macroporous boron nitride fiber made in accordance with an embodiment of the present invention;
fig. 3 is SEM photographs of macroporous boron nitride fibers prepared in two comparative examples.
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The macroporous boron nitride fiber provided by the invention is prepared by using loofah sponge as a carbon source template and replacing carbon elements in the loofah sponge by a gas-phase boron source and a nitrogen source under a high-temperature condition, wherein the obtained macroporous boron nitride fiber has the same pore structure characteristics as the original loofah sponge matrix.
The macroporous boron nitride fiber is formed by taking a natural plant loofah sponge as a carbon source template, and by adopting a replacement mode, boron nitride is used for replacing carbon elements in the loofah sponge, so that a pore structure which is the same as that of an original loofah sponge matrix can be obtained, the structural characteristics of the original loofah sponge matrix can be kept, the matrix has the physical and chemical properties of the boron nitride, the defects of agglomeration, etching and residue caused in the process of removing the template in the process of coating the template by a target material can be avoided, the macroporous boron nitride fiber has extremely large specific surface area, ultra-strong adsorption capacity and surface activity, has quick and efficient adsorption capacity on heavy metal ions, dyes, toxic gases and organic pollutants in the environment, and has strong thermal stability, chemical stability and oxidation resistance.
Furthermore, the macroporous boron nitride fiber adopts loofah sponge as a raw material, has cheap and easily-obtained raw material source, very low cost and light weight, has a natural pore structure, does not need to process the raw material, has larger yield of products, is relatively easy to regenerate the adsorbed material, does not generate harmful substances in the preparation process, and is safe and environment-friendly.
The invention also provides a preparation method of the macroporous boron nitride fiber, which comprises the following steps:
s1 cleaning retinervus Luffae fructus with water and ethanol respectively, and drying.
In the step, the loofah sponge is alternately cleaned by water and ethanol for multiple times by adopting ultrasound respectively to remove impurities on the loofah sponge until the loofah sponge is completely cleaned, and then the loofah sponge is dried for 20-30h at the temperature of 70-100 ℃.
S2, weighing the boron source and the loofah sponge according to the proportion, then respectively placing the boron source and the cleaned loofah sponge in a double-layer crucible, wherein the boron source is placed in the lower layer of the double-layer crucible, the cleaned loofah sponge is placed in the upper layer of the double-layer crucible, and then the double-layer crucible is placed in a high-temperature furnace.
In the step, the boron source is boron nitride, so that the carbon element can be completely replaced under the subsequent replacement reaction temperature condition, and the situation that Boron Carbon Nitride (BCN) exists due to incomplete replacement at low temperature is avoided.
In actual operation, the dried loofah sponge can be cut into small pieces, which is beneficial to accelerating the replacement process. Then weighing boron nitride and loofah sponge according to the ratio of 2-4:1, respectively placing the boron nitride and the loofah sponge on the lower layer and the upper layer of the double-layer crucible, isolating the boron nitride and the loofah sponge from each other, then placing the double-layer crucible in a high-temperature furnace, and sealing.
In the double-layer crucible arranged in the step, the bottom of the upper layer of the crucible is provided with a small hole, so that an airflow channel is formed between the upper layer and the lower layer of the double-layer crucible, boron oxide of the lower layer forms vapor phase evaporation after being heated at high temperature under the high-temperature condition, and the boron oxide is communicated with the upper layer through the small hole and is used for replacing carbon elements in the loofah sponge arranged on the upper layer of the crucible. In addition, the top of the upper layer of the crucible is also provided with a cover plate, the side walls of the upper layer and the lower layer of the crucible are provided with at least one small hole, wherein the small hole on the side wall of the lower layer of the crucible can be used for enabling nitrogen to flow in and be used as a carrier gas and a nitrogen source to take away a boron source evaporated in a gas phase, and then the nitrogen enters the upper layer through the small hole on the bottom of the upper layer and is replaced with carbon element in the silk melon network on the upper layer to. Because the top of the upper layer of the crucible is provided with the cover plate, after the reaction is finished, gas can be emitted outwards along the small holes on the side wall of the upper layer.
S3 introducing nitrogen source into the high temperature furnace, heating to 1300 ℃ and 1600 ℃, keeping for a period of time, and naturally cooling to room temperature to finish the replacement of carbon elements in the boron nitride and the loofah sponge, thereby obtaining the white loofah sponge skeleton-shaped white boron nitride fiber.
In the step, the nitrogen source introduced into the high-temperature furnace is N2(Nitrogen), the flow rate is 300-500 sccm. During the reaction, the N2The temperature can be raised from room temperature to 1300-1600 ℃ at the temperature raising rate of 5 ℃/min, and then N is added2The flow rate is increased to 1200-1600sccm, the temperature is maintained for 5-6h, and then the temperature is naturally decreased to room temperature.
Introducing nitrogen N into a high-temperature furnace2The purpose of the method is to be used as carrier gas to load a boron source into an upper crucible to contact loofah sponge so as to finish replacement, simultaneously, nitrogen can provide a nitrogen source for the replacement reaction to participate in the reaction process, when the temperature in a high-temperature furnace reaches 1300-2The increased flow can provide sufficient nitrogen source for the displacement reaction, is favorable for accelerating the displacement reaction, shortens the reaction time, and can ensure the smooth proceeding of the reaction process and the completeness of the reaction process.
The temperature of the high-temperature furnace is selected between 1300-1600 ℃, and in the reaction process, along with the increase of the replacement temperature, the pore structure of the boron nitride fiber begins to become small, and the specific surface area becomes large. During preparation, the temperature can be adjusted according to the requirement, and the size of the pore structure of the replaced boron nitride fiber can be adjusted so as to adjust the specific surface area of the prepared boron nitride fiber. Within the temperature range, the higher the temperature is, the higher the nitridation degree of the loofah sponge is, the more thorough the replacement is, and the higher the purity of the boron nitride fiber is. However, when the temperature exceeds 1600 ℃, the pore channels in the boron nitride fibers gradually begin to collapse, and the specific surface area begins to become smaller. When the temperature in the high temperature furnace is selected to be between 1400 ℃ and 1500 ℃, better replacement effect and specific surface area can be achieved.
Preparation examples:
(1) ultrasonically cleaning retinervus Luffae fructus with water and ethanol respectively for at least three times, drying at 80 deg.C for 24 hr, and cutting into small pieces;
(2) weighing boron oxide (a boron source) and loofah sponge according to a mass ratio of 3:1, then respectively placing the boron oxide and the loofah sponge into a double-layer boron nitride crucible, wherein the boron oxide is laid on the lower layer of the crucible, the loofah sponge is placed on the upper layer of the crucible, then placing the double-layer crucible into a high-temperature tubular furnace, and sealing the tubular furnace;
(3) introducing N into the high-temperature tube furnace2(Nitrogen source), N2The flow rate is 400sccm, the temperature in the furnace is raised from room temperature to about 1400 ℃ or 1500 ℃ at the temperature raising rate of 5 ℃/min, and then N is added2The flow rate was increased to 1500sccm for 5 h.
After the reaction is finished, the temperature of the tubular furnace is naturally reduced to room temperature, and the white loofah sponge skeleton-shaped white boron nitride fiber shown in figure 1 is obtained.
And (3) detection results:
referring to fig. 1, from the photo of the prepared macroporous boron nitride fiber, the effect of replacing carbon element in the loofah sponge by adopting the preparation embodiment of the invention is very good, the original structural characteristics of the loofah sponge matrix are completely maintained, and the fiber pores are uniformly distributed;
as shown in FIG. 2, the XRD diffractogram of the porous boron nitride prepared at the temperature of about 1500 ℃ in the embodiment of the invention shows that the diffraction peaks (002), (100) and (110) are completely consistent with the XRD standard peaks of the hexagonal boron nitride.
Referring to fig. 3 a-3 b, SEM images of porous boron nitride obtained at temperatures around 1300 c and above 1600 c for two comparative examples are shown, which show that the cross-section is densely populated with pores having a pore size on the order of microns and that they are found to have surface wrinkles, indicating that the purity of the boron nitride fibers and the fiber pore structure are not particularly desirable.
The above-mentioned embodiments of the present invention and the accompanying drawings are only part of the preferred embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art may make modifications, equivalents and improvements without departing from the spirit of the present invention.
Claims (9)
1. The macroporous boron nitride fiber is characterized in that loofah sponge is used as a carbon source template, and carbon elements in the loofah sponge are replaced by a boron source and a nitrogen source, so that the macroporous boron nitride fiber with the same pore structure as the original loofah sponge matrix is obtained.
2. The method of making macroporous boron nitride fiber of claim 1, comprising the steps of:
cleaning retinervus Luffae fructus with water and ethanol respectively, and drying;
weighing a boron source and dried loofah sponge according to a ratio, and then respectively placing the boron source and the loofah sponge in a double-layer crucible, wherein the boron source is placed at the lower layer of the double-layer crucible, the loofah sponge is placed at the upper layer of the double-layer crucible, and then the double-layer crucible is placed in a high-temperature furnace;
introducing a nitrogen source into the high-temperature furnace, raising the temperature to 1300-1600 ℃, keeping the temperature for a period of time, and naturally cooling to room temperature to obtain the white loofah skeleton-shaped white boron nitride fiber.
3. The method of preparing macroporous boron nitride fibers of claim 2, wherein the boron source is boron oxide and the nitrogen source is N2。
4. The method for preparing macroporous boron nitride fiber according to claim 2, wherein the retinervus Luffae fructus is washed with water and ethanol by ultrasonic wave alternately for multiple times, and then dried at 70-100 deg.C for 20-30 h.
5. The method for preparing macroporous boron nitride fiber according to claim 2 or 3, wherein the boron source and the loofah sponge are weighed according to the ratio of 2-4: 1.
6. The method for preparing macroporous boron nitride fiber according to claim 2 or 3, wherein the flow rate of the nitrogen source introduced into the high temperature furnace is 300-500 sccm.
7. The method for preparing macroporous boron nitride fiber according to claim 6, wherein the temperature of the nitrogen source introduced into the high temperature furnace is increased from room temperature to 1300-1600 ℃ at a rate of 5 ℃/min.
8. The method for preparing macroporous boron nitride fiber as claimed in claim 7, wherein the temperature of the high temperature furnace is 1400-1500 ℃.
9. The method for preparing macroporous boron nitride fiber as claimed in claim 7, wherein the nitrogen source introduced into the high temperature furnace is increased to 1300-1600 ℃ and then the flow rate of the nitrogen source is increased to 1200-1600sccm and kept for 5-6h, and then the temperature is naturally decreased to room temperature.
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| CN111876750B (en) * | 2020-07-30 | 2021-03-26 | 中国人民解放***箭军工程大学 | Preparation method of super-hydrophobic filter screen with boron nitride nano coral growing on surface |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392941A1 (en) * | 1989-04-13 | 1990-10-17 | Rhone-Poulenc Chimie | Use of boron and nitrogen-based polymers as precursors for boronnitride-based ceramics thus obtained |
| CN103088464A (en) * | 2013-02-01 | 2013-05-08 | 湖北工业大学 | Preparation method of porous boron nitrite fibers |
| CN103922296A (en) * | 2014-04-30 | 2014-07-16 | 辽宁大学 | Spherical boron nitride and application thereof |
| CN103964403A (en) * | 2014-04-08 | 2014-08-06 | 南京航空航天大学 | Preparation method of three-dimensional porous hexagonal boron nitride |
| CN104803362A (en) * | 2015-04-10 | 2015-07-29 | 复旦大学 | Preparation method of hexagonal boron nitride powder and three-dimensional boron nitride |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392941A1 (en) * | 1989-04-13 | 1990-10-17 | Rhone-Poulenc Chimie | Use of boron and nitrogen-based polymers as precursors for boronnitride-based ceramics thus obtained |
| CN103088464A (en) * | 2013-02-01 | 2013-05-08 | 湖北工业大学 | Preparation method of porous boron nitrite fibers |
| CN103964403A (en) * | 2014-04-08 | 2014-08-06 | 南京航空航天大学 | Preparation method of three-dimensional porous hexagonal boron nitride |
| CN103922296A (en) * | 2014-04-30 | 2014-07-16 | 辽宁大学 | Spherical boron nitride and application thereof |
| CN104803362A (en) * | 2015-04-10 | 2015-07-29 | 复旦大学 | Preparation method of hexagonal boron nitride powder and three-dimensional boron nitride |
Non-Patent Citations (1)
| Title |
|---|
| 新型多孔氮化硼材料;刘栋;《化学进展》;20130731;第25卷(第7期);第1113-1121页 * |
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