CN111137865A - A method for realizing different superwetting properties of boron nitride aerogels by supramolecular assembly - Google Patents
A method for realizing different superwetting properties of boron nitride aerogels by supramolecular assembly Download PDFInfo
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0646—Preparation by pyrolysis of boron and nitrogen containing compounds
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Abstract
本发明涉及材料表面润湿性和纳米多孔材料领域，具体为一种利用超分子组装实现氮化硼气凝胶不同超浸润性的方法。选用三聚氰胺、甲代三聚氰胺和硼酸为分子组元制备出超分子凝胶，再经冷冻干燥以及高温处理可得到最终的氮化硼气凝胶。通过调节形成超分子凝胶的分子组元的类型和比例，可以影响最终所得氮化硼气凝胶的微观形貌，进而使其表现不同的超浸润性。本发明提供的方法可制备出具有不同原生超浸润性的氮化硼气凝胶，有望在初始阶段对材料最终的润湿性进行设计，所述的方法具有可操作性强，工艺简单且易于重复的优点。The invention relates to the field of material surface wettability and nano-porous materials, in particular to a method for realizing different super-wetting properties of boron nitride aerogel by utilizing supramolecular assembly. The supramolecular gel was prepared by using melamine, methyl melamine and boric acid as molecular components, and then the final boron nitride aerogel could be obtained by freeze-drying and high temperature treatment. By adjusting the types and proportions of the molecular components forming the supramolecular gel, the microscopic morphology of the boron nitride aerogel finally obtained can be influenced, thereby making it exhibit different superwetting properties. The method provided by the invention can prepare boron nitride aerogels with different primary super-wetting properties, and is expected to design the final wettability of the material in the initial stage. The method has strong operability, simple process and easy The advantage of repetition.
Description
Technical Field
The invention relates to the field of material surface wettability and nano porous materials, in particular to a method for realizing different super wettability of boron nitride aerogel by utilizing supermolecule assembly.
Background
Inspired by the nature, the super-wetting property attracts people's attention for many years, and researches have fully shown the huge application potential in the aspects of energy, environment, information and the like. In order to obtain materials with ultra-wettability, complex treatments are often used, such as: the method comprises the steps of irradiating, coating, etching and the like to change the surface energy or surface appearance of the material so as to regulate and control the wettability of the material, and the method can be fundamentally summarized as relying on the acquired treatment of the material to obtain different super wettability. However, the original super-wettability of the material and the design of the final wettability in the initial stage are very challenging issues, and related researches are rare.
Due to the advantages of excellent chemical stability, high thermal conductivity, excellent biocompatibility and the like, the boron nitride nano material has wide application in the aspects of environmental management, thermal management, biological materials and the like, and has important significance in researching the wettability. Previous research on boron nitride nanomaterials has been directed primarily to low dimensional forms of boron nitride, such as: pakdel et al obtained boron nitride Nano-films with different super-wettability by plasma irradiation or a method of adjusting chemical vapor deposition experimental parameters (ACS Nano 2011,5, 6507-. For three-dimensional porous boron nitride, most documents only show that the boron nitride has super-hydrophobic characteristics, but the design and the control of the wettability of the boron nitride are rarely deeply discussed. As a porous material with a nanometer framework, the boron nitride aerogel integrates the advantages of micro and macro materials, has attracted the interest of the scientific community in recent years, has been reported to have the characteristics of extremely low dielectric constant, super elasticity and the like through research, and has great application potential in various fields. However, no research on realizing different super wettability is found so far, and a regulation method of wettability is rarely reported. Only one document has been found so far to mention that boron nitride aerogel can be made relatively hydrophilic from a super-hydrophobic state by means of ultraviolet irradiation, but is far from the super-hydrophilic state; in addition, such a relatively hydrophilic state is difficult to maintain for a long time, and the contact angle starts to increase in a short time and returns to the hydrophobic state again (nanoscales 2015,7, 10449-10458). It is noted that for porous boron nitride, expensive and toxic organic precursors are often chosen for the preparation, such as: borazine, borazane, and the like. For boron nitride aerogel, which is a nano-scale porous material with a framework, the existing preparation technology mostly uses existing aerogel (for example, graphene aerogel or silica aerogel, etc.) as a template, and performs element replacement by a gas phase method to obtain the final aerogel. Expensive raw materials and complicated preparation processes also become limiting factors for popularization and application of boron nitride related porous materials.
In comparison with the expensive raw materials and complex processes mentioned above, in the preparation of boron nitride powder, cheap raw materials such as urea, melamine, boric acid and borax are often selected for a long time. Especially for both melamine and boric acid, they form white substances upon cooling after dissolution in water. The back of this phenomenon corresponds to the supramolecular assembly process, which uses non-covalent bonding between the components to produce spontaneous alignment and assembly, and different components and solvents can be selected to obtain completely different morphologies. In recent years, the role of supramolecular assembly in the preparation of inorganic materials has become increasingly prominent, for example: when preparing the graphite type carbon nitride nano material, people obtain supermolecule aggregates with different micro-morphologies by means of the characteristic that supermolecule is formed by melamine and other substances in a wet chemical stage, and then obtain the final carbon nitride by high-temperature conversion. Due to the controlled process in the wet-chemical stage, the final product obtained by the method has an inherent diverse microstructure, which also results in the diversity and tunability of the obtained material in specific properties. The boron nitride material and the carbon nitride material both use melamine in raw materials, and can also adjust the final performance of the material by fully playing the advantages of supramolecular assembly, but the realization of different super wettability of the boron nitride material by a supramolecular assembly method has not been reported, and for other material systems, the research of using a supramolecular assembly preparation idea for wettability regulation and control has not been available.
Disclosure of Invention
The invention aims to provide a method for realizing different super-wettability of boron nitride aerogel by utilizing supramolecular assembly, which can influence the microstructure of the boron nitride aerogel obtained by high-temperature conversion by simply adjusting the type and the proportion of molecular components forming supramolecular gel, so that the boron nitride aerogel shows different native super-wettability, and the method makes the final wettability of the material designed from the initial stage possible.
The technical scheme of the invention is as follows:
a method for realizing different super-wettability of boron nitride aerogel by utilizing supermolecule assembly influences the microstructure of the boron nitride aerogel obtained by high-temperature conversion by regulating the type and the proportion of molecular components forming the supermolecule gel, so that the boron nitride aerogel shows different native super-wettability, and comprises the following specific steps:
1) preparation of supramolecular gel: dissolving melamine and boric acid in a molar ratio of 1: 3-1: 9 in deionized water at 75-95 ℃ and stirring for 1-10 hours; dissolving melamine, methyl melamine and boric acid in a molar ratio of 1:1: 4-1: 1:12 in deionized water at 75-95 ℃ and stirring for 1-10 hours; then, pouring the series of solutions into different containers, and cooling at room temperature to form supramolecular gel;
2) drying the supramolecular gel: freezing the supramolecular gel in the step 1) for 12-24 hours at-25 to-45 ℃ respectively, and then drying in a vacuum environment;
3) high-temperature treatment: and (3) putting the frozen and dried supermolecule gel obtained in the step 2) into an atmosphere furnace, and preserving the heat for 3-5 hours at 1300-1500 ℃ to obtain the boron nitride aerogel with different super-wettability.
The method for realizing different super-wettability of the boron nitride aerogel by utilizing supermolecule assembly is characterized in that the boron nitride aerogel obtained by taking melamine and boric acid as raw materials through high-temperature conversion has super-hydrophilicity and super-oleophylic property, namely super-amphiphilicity; melamine, methyl melamine and boric acid are used as raw materials: when the molar ratio is 1:1: 4-1: 1:7, the boron nitride aerogel obtained through high-temperature conversion shows super-hydrophobic and super-oleophilic properties; when the molar ratio is 1:1: 9-1: 1:12, the boron nitride aerogel obtained through high-temperature conversion shows the super-amphiphilic property again.
The method for realizing different super-wettability of the boron nitride aerogel by utilizing supermolecule assembly is characterized in that the super-hydrophobic and super-oleophylic boron nitride aerogel prepared by taking melamine, methyl melamine and boric acid as raw materials has a bird-nest-shaped microstructure, the structure is composed of fiber clusters formed by short fibers with the diameters of 0.5-1 mu m and the lengths of 10-30 mu m, and the diameters of macropores formed by lapping the fiber clusters are 20-60 mu m.
According to the method for realizing different super-wettability of the boron nitride aerogel by utilizing supermolecule assembly, the super-wettability state of the obtained boron nitride aerogel can be kept for more than three months, and good robustness is shown.
The method for realizing different super-wettability of the boron nitride aerogel by utilizing supermolecule assembly is characterized in that in the step 1), the total concentration of each prepared solution is 25-55 mg/ml.
The method for realizing different super-wettability of the boron nitride aerogel by utilizing supramolecular assembly comprises the step 3), wherein the atmosphere used by the atmosphere furnace is argon or nitrogen.
The design idea of the invention is as follows:
the invention selects melamine, methyl melamine and boric acid as molecular components to prepare the super-molecular gel, and then the final boron nitride aerogel can be obtained through freeze drying and high-temperature treatment. According to the invention, the micro-morphology of the finally obtained boron nitride aerogel can be influenced by adjusting the type and the proportion of the molecular components forming the supramolecular gel, so that the boron nitride aerogel can show different super-wettability. The method provided by the invention can be used for preparing the boron nitride aerogel with different native super-wettability, and is expected to design the final wettability of the material at the initial stage.
The invention has the advantages and beneficial effects that:
1. the invention utilizes supermolecule assembly to prepare boron nitride aerogel with different native super-wettability, and particularly influences the microstructure of the boron nitride aerogel obtained by high-temperature conversion by simply adjusting the type and proportion of molecular components forming the supermolecule gel, so that the boron nitride aerogel shows different native super-wettability.
2. The invention provides a method for effectively obtaining and adjusting the super-wetting state of boron nitride aerogel, which gets rid of the complicated treatment procedures of coating, irradiation, etching and the like related to the traditional wetting adjustment method.
3. The preparation method is simple in preparation flow, environment-friendly in process and easy to realize industrialization.
4. The super-wetting state of the boron nitride aerogel obtained by the invention can be maintained for several months, the boron nitride aerogel shows good robustness and has great application prospects in the fields of environmental management, biological materials, water-oil separation and the like.
Drawings
Fig. 1 is a physical diagram of boron nitride aerogels with different shapes and sizes prepared by a supramolecular assembly method.
Fig. 2 is an X-ray diffraction spectrum of a boron nitride aerogel prepared from melamine (M) and boric acid (B) as raw materials at a molar ratio of M: B of 1: 6.
Fig. 3(a) to (c) show scanning electron micrographs of boron nitride aerogel obtained from melamine (M) and boric acid (B) as raw materials at a molar ratio of M: B of 1:6 and the results of contact angle measurement (a), scanning electron micrographs of boron nitride aerogel obtained from melamine (M), melamine formate (M), and boric acid (B) as raw materials at a molar ratio of M: B of 1:1:6 and the results of contact angle measurement (B), and scanning electron micrographs of boron nitride aerogel obtained from M: B of 1:1:10 and the results of contact angle measurement (c), respectively.
Fig. 4(a) - (b) are graphs comparing wettability to initial state after three months for boron nitride aerogel with super-amphiphilicity (a) and boron nitride aerogel with super-hydrophobic/super-oleophilic properties (b).
Detailed Description
In the specific implementation process, the invention influences the microstructure of the boron nitride aerogel obtained by high-temperature conversion by regulating the type and the proportion of molecular components forming the supramolecular gel, so that the boron nitride aerogel shows different super wettability. Moreover, the super-wetting state can be maintained for months, and good robustness is shown.
The invention is further described below by means of figures and examples.
Example 1
In the embodiment, 100ml of deionized water is firstly measured and added into a beaker, then melamine and boric acid are added according to a molar ratio of 1:6, the total concentration is set to be 50mg/ml, and specifically 1.269g of melamine and 3.731g of boric acid are taken; dissolving them in water bath at 95 deg.C, stirring for 10 hr, packaging, pouring into different containers, cooling at room temperature, and observing the formation of white supramolecular gel; then, freezing the generated supramolecular gel at-25 ℃ for 24 hours, and immediately drying the supramolecular gel in a vacuum environment; and (3) putting the dried white gel into a tubular atmosphere furnace, and preserving the heat for 4 hours at 1400 ℃ in a nitrogen environment to obtain the final boron nitride aerogel, which is shown in figure 1.
As shown in fig. 2, the X-ray diffraction spectrum of the finally obtained boron nitride aerogel shows that the prepared boron nitride aerogel is pure phase hexagonal boron nitride, and the crystallinity is comparable to commercial grade powder. As can be seen from the scanning electron micrograph and the contact angle test results shown in fig. 3(a), the microstructure of the boron nitride aerogel obtained in this example is in a fiber-interlaced state, the wetting angles for water and oil are both 0 °, and the boron nitride aerogel shows super-hydrophilic and super-oleophilic characteristics, i.e., super-amphiphilic.
Example 2
In the embodiment, 100ml of deionized water is firstly measured and added into a beaker, and then melamine, melamine A and boric acid are added according to the molar ratio of 1:1:6, the total concentration is set to be 30mg/ml, and specifically 0.608g of melamine, 0.603g of melamine A and 1.789g of boric acid are taken; dissolving them in water bath at 80 deg.C, stirring for 5 hr, packaging, pouring into different containers, and cooling at room temperature to obtain white supramolecular gel; then, freezing the generated supramolecular gel at-35 ℃ for 18 hours, and immediately drying the supramolecular gel in a vacuum environment; and (3) putting the dried supramolecular gel into a tubular atmosphere furnace, and preserving the heat for 5 hours at 1300 ℃ in an argon environment to obtain the final boron nitride aerogel.
As shown in fig. 3(b), scanning electron micrographs of the obtained boron nitride aerogel and the contact angle test results thereof. According to the figure, the microstructure of the boron nitride aerogel prepared under the condition is a nest-shaped fiber staggered structure, the structure is formed by fiber clusters formed by short fibers with the diameters of 0.5-1 mu m and the lengths of 10-30 mu m, and the diameters of large holes formed by lapping the fiber clusters are 20-60 mu m. The contact angle test results show that the contact angles of the water and the oil are 152.5 degrees and 0 degree respectively, and the super-hydrophobic and super-oleophilic characteristics are shown.
Example 3
In the embodiment, 100ml of deionized water is firstly measured and added into a beaker, then melamine, melamine A and boric acid are added according to a molar ratio of 1:1:10, the total concentration is set to be 40mg/ml, and specifically 0.580g of melamine, 0.576g of melamine A and 2.844g of boric acid are taken; dissolving them in water bath at 90 deg.C, stirring for 1 hr, packaging, pouring into different containers, and cooling at room temperature to obtain white supramolecular gel; then, freezing the generated supramolecular gel at-45 ℃ for 12 hours, and immediately drying the supramolecular gel in a vacuum environment; and finally, putting the dried supramolecular gel into a tubular atmosphere furnace, and preserving the heat for 3 hours at 1500 ℃ in a nitrogen environment to obtain the final boron nitride aerogel.
As shown in fig. 3(c), scanning electron micrographs of the obtained boron nitride aerogel and the contact angle test results thereof. As can be seen from the figure, the microstructure of the boron nitride aerogel prepared under the condition is similar to that of the sample in example 1, and is a relatively flat staggered fibrous structure, and the contact angle test result shows that the contact angles of the boron nitride aerogel to water and oil are both 0 degrees, and the boron nitride aerogel shows the characteristic of super-amphipathy again.
The embodiment result shows that the boron nitride aerogel has different primary super-wettability by utilizing the supermolecule assembly, the microstructure of the boron nitride aerogel obtained by high-temperature transformation is influenced by adjusting the types and the initial proportions of the molecular components forming the supermolecule gel, the boron nitride aerogel is converted between super-amphiphilic property and super-hydrophobic/super-oleophilic property, and the complex treatment procedures of coating, irradiation, etching and the like related to the traditional wettability adjusting method are eliminated. The invention has the advantages of cheap preparation raw materials, simple preparation process, environment-friendly process and easy industrialization. As shown in fig. 4(a) - (b), the boron nitride aerogel with super-amphiphilicity and the corresponding super-wetting state of the boron nitride aerogel with super-hydrophobic/super-oleophilic property can both be maintained for more than three months, show good robustness, and have great application prospects in the fields of environmental governance, biological materials, water-oil separation and the like.
Claims (6)
1. A method for realizing different super-wettability of boron nitride aerogel by utilizing supermolecule assembly is characterized in that the microstructure of the boron nitride aerogel obtained by high-temperature conversion is influenced by regulating the type and the proportion of molecular components forming the supermolecule gel, so that the boron nitride aerogel shows different native super-wettability, and the method comprises the following specific steps:
1) preparation of supramolecular gel: dissolving melamine and boric acid in a molar ratio of 1: 3-1: 9 in deionized water at 75-95 ℃ and stirring for 1-10 hours; dissolving melamine, methyl melamine and boric acid in a molar ratio of 1:1: 4-1: 1:12 in deionized water at 75-95 ℃ and stirring for 1-10 hours; then, pouring the series of solutions into different containers, and cooling at room temperature to form supramolecular gel;
2) drying the supramolecular gel: freezing the supramolecular gel in the step 1) for 12-24 hours at-25 to-45 ℃ respectively, and then drying in a vacuum environment;
3) high-temperature treatment: and (3) putting the frozen and dried supermolecule gel obtained in the step 2) into an atmosphere furnace, and preserving the heat for 3-5 hours at 1300-1500 ℃ to obtain the boron nitride aerogel with different super-wettability.
2. The method for realizing different super wettability of boron nitride aerogel by using supramolecular assembly as claimed in claim 1, wherein the boron nitride aerogel obtained by high temperature conversion of melamine and boric acid as raw materials shows super hydrophilic and super oleophilic characteristics, i.e. super amphiphilic characteristics; melamine, methyl melamine and boric acid are used as raw materials: when the molar ratio is 1:1: 4-1: 1:7, the boron nitride aerogel obtained through high-temperature conversion shows super-hydrophobic and super-oleophilic properties; when the molar ratio is 1:1: 9-1: 1:12, the boron nitride aerogel obtained through high-temperature conversion shows the super-amphiphilic property again.
3. The method for realizing different super wettability of the boron nitride aerogel by utilizing supramolecular assembly as claimed in claim 2, wherein the super-hydrophobic and super-oleophilic boron nitride aerogel prepared by using melamine, melamine A and boric acid as raw materials has a bird-nest-shaped microstructure, the structure is composed of fiber clusters formed by short fibers with the diameter of 0.5-1 μm and the length of 10-30 μm, and the diameter of macropores formed by lapping the fiber clusters is 20-60 μm.
4. The method for realizing different super-wettability of the boron nitride aerogel by utilizing supramolecular assembly as claimed in claim 1, wherein the super-wettability state of the obtained boron nitride aerogel can be maintained for more than three months, and good robustness is shown.
5. The method for realizing different super-wettability of the boron nitride aerogel by utilizing supramolecular assembly as claimed in claim 1, wherein in the step 1), the total concentration of each prepared solution is 25-55 mg/ml.
6. The method for realizing different super wettability of boron nitride aerogel by supramolecular assembly as claimed in claim 1, wherein in step 3), the atmosphere used in the atmosphere furnace is argon or nitrogen.
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