阅读说明：本技术 一种α-AlH3/Al2O3/C60双壳层结构复合物、合成方法及应用 (alpha-AlH3/Al2O3/C60Double-shell structure compound, synthesis method and application ) 是由 蒋周峰 赵凤起 安亭 杨燕京 李辉 张明 张建侃 姜一帆 李娜 于 2020-07-24 设计创作，主要内容包括：本发明公开了一种α-AlH<Sub>3</Sub>/Al<Sub>2</Sub>O<Sub>3</Sub>/C<Sub>60</Sub>双壳层结构复合物、合成方法及应用,α-AlH<Sub>3</Sub>/Al<Sub>2</Sub>O<Sub>3</Sub>/C<Sub>60</Sub>双壳层结构复合物,由内到外,所述的复合物包括内核,包裹内核的第一壳层,包裹第一壳层的第二壳层；所述的内核为α-AlH<Sub>3</Sub>核,所述的第一壳层为Al<Sub>2</Sub>O<Sub>3</Sub>层,所述的第二壳层为改性C<Sub>60</Sub>层；改性C<Sub>60</Sub>层为C<Sub>60</Sub>上携带羧基形成的材料层。与α-AlH<Sub>3</Sub>对比,本方法所合成的α-AlH<Sub>3</Sub>/Al<Sub>2</Sub>O<Sub>3</Sub>/C<Sub>60</Sub>双壳层结构复合物热稳定性能显著提高,而且复合物结构中C<Sub>60</Sub>含量低于1％。本发明的α-AlH<Sub>3</Sub>/Al<Sub>2</Sub>O<Sub>3</Sub>/C<Sub>60</Sub>双壳层结构复合物实现了在酸洗处理方法基础上进一步提升α-AlH<Sub>3</Sub>热稳定性的目的,合成得到的α-AlH<Sub>3</Sub>/Al<Sub>2</Sub>O<Sub>3</Sub>/C<Sub>60</Sub>双壳层结构复合物可作为固体推进剂燃料,双壳层结构的制备过程于常温进行,制备方法安全可靠,适用于大规模生产。(The invention discloses an alpha-AlH 3 /Al 2 O 3 /C 60 Double-shell structure compound, synthetic method and application, alpha-AlH 3 /Al 2 O 3 /C 60 The composite with the double-shell structure comprises an inner core, a first shell layer wrapping the inner core and a second shell layer wrapping the first shell layer from inside to outside; the kernel is alpha-AlH 3 A core, the first shell layer is Al 2 O 3 Layer, the second shell layer is modified C 60 A layer; modification C 60 Layer is C 60 A material layer formed by carrying carboxyl. With alpha-AlH 3 By contrast, the alpha-AlH synthesized by the method 3 /Al 2 O 3 /C 60 The thermal stability of the compound with a double-shell structure is obviously improved, and C in the compound structure 60 The content is less than 1%. alpha-AlH of the invention 3 /Al 2 O 3 /C 60 The double-shell structure compound realizes the further promotion of alpha-AlH on the basis of the acid pickling treatment method 3 Purpose of thermal stability, alpha-AlH obtained by synthesis 3 /Al 2 O 3 /C 60 The double-shell structure compound can be used as a solid propellant fuel, the preparation process of the double-shell structure is carried out at normal temperature, and the preparation method is safe and reliable and is suitable for large-scale production.)

1. alpha-AlH₃/Al₂O₃/C₆₀The double-shell structure compound is characterized in that the compound comprises an inner core, a first shell wrapping the inner core and a second shell wrapping the first shell from inside to outside;

the kernel is alpha-AlH₃A core, the first shell layer is Al₂O₃Layer, the second shell layer is modified C₆₀A layer;

modification C₆₀Layer is C₆₀A material layer formed by carrying carboxyl.

2. alpha-AlH according to claim 1₃/Al₂O₃/C₆₀The double-shell structure compound is characterized in that the diameter of the inner core is 200 nm-40 um;

the thickness of the first shell layer is 5-30 nm;

the thickness of the second shell layer is 1-15 nm.

3. alpha-AlH according to claim 1 or 2₃/Al₂O₃/C₆₀A double shell structure complex characterized by alpha-AlH₃/Al₂O₃/C₆₀The preparation method of the double-shell structure compound comprises the following steps:

cleaning alpha-AlH with dilute hydrochloric acid solution₃Obtaining alpha-AlH₃/Al₂O₃Core/shell materials of construction, alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀Stirring and dispersing in a toluene/tetrahydrofuran mixed solvent to obtain the alpha-AlH₃/Al₂O₃/C₆₀A double shell structured composite.

4. alpha-AlH according to claim 3₃/Al₂O₃/C₆₀The double-shell structure compound is characterized in that the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min.

5. alpha-AlH according to claim 3₃/Al₂O₃/C₆₀A double shell structure complex characterized by alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀The mass ratio of (A) to (B) is 5: 1; the volume ratio of toluene to tetrahydrofuran in the toluene/tetrahydrofuran mixed solvent is 2; the stirring and dispersing time is 4-12 h.

6. alpha-AlH according to claim 3₃/Al₂O₃/C₆₀The compound with a double-shell structure is characterized in that the modified C₆₀The preparation method comprises the following steps:

collecting 170mg of 4-carboxybenzaldehyde and 150mg of C₆₀And 90mg sarcosine in turn in 50ml chlorobenzene; refluxing the chlorobenzene solution at 135 ℃ for 16h under nitrogen atmosphere; the solvent component in the product was removed by rotary evaporation to obtain a dark brown powder, which was then dispersed in a toluene/tetrahydrofuran mixed solvent (v/v ═ 2), and separated by silica gel column chromatography to obtain brown modified C₆₀And (3) sampling.

7. alpha-AlH₃/Al₂O₃/C₆₀The method for synthesizing the double-shell structure compound is characterized by comprising the following steps of:

cleaning alpha-AlH with dilute hydrochloric acid solution₃Obtaining alpha-AlH₃/Al₂O₃Core/shell materials of construction, alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀Stirring and dispersing in a toluene/tetrahydrofuran mixed solvent to obtain the alpha-AlH₃/Al₂O₃/C₆₀A double shell structured composite.

8. alpha-AlH according to claim 7₃/Al₂O₃/C₆₀The method for synthesizing the double-shell structure compound is characterized in that the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min;

α-AlH₃/Al₂O₃core/shell structure material and modified C₆₀The mass ratio of (A) to (B) is 5: 1; the volume ratio of toluene to tetrahydrofuran in the toluene/tetrahydrofuran mixed solvent is 2; the stirring and dispersing time is 4-12 h.

9. alpha-AlH according to claim 7 or 8₃/Al₂O₃/C₆₀The method for synthesizing the compound with the double-shell structure is characterized in that the modified C₆₀The preparation method comprises the following steps:

collecting 170mg of 4-carboxybenzaldehyde and 150mg of C₆₀And 90mg sarcosine in turn in 50ml chlorobenzene; refluxing the chlorobenzene solution at 135 ℃ for 16h under nitrogen atmosphere; the solvent component in the product was removed by rotary evaporation to obtain a dark brown powder, which was then dispersed in a toluene/tetrahydrofuran mixed solvent (v/v ═ 2), and separated by silica gel column chromatography to obtain brown modified C₆₀And (3) sampling.

10. alpha-AlH according to any one of claims 1 to 6₃/Al₂O₃/C₆₀Use of a double shell structure composite for the preparation of a solid propellant fuel.

Technical Field

The invention belongs to the field of solid fuels, and particularly relates to alpha-AlH₃/Al₂O₃/C₆₀Double-shell structure compound, synthesis method and application, and alpha-AlH can be remarkably improved by using double-shell structure₃Thermal stability of (3).

Background

Hydrogen is introduced in the combustion process of the solid propellant, so that the average relative molecular mass of the fuel gas can be effectively reduced; meanwhile, the high combustion heat value of the hydrogen is beneficial to improving the temperature of the combustion chamber and the specific impulse. Aluminum trihydride is a light metal hydride with a relatively high hydrogen content, up to 10.08%, has a hydrogen storage density of 148g/L, twice that of liquid hydrogen (70.8g/L), has a higher heat of combustion value than aluminum powder, and is an ideal solid propellant fuel. At present, AlH₃A total of 7 different crystal forms include: α, α', β, γ, ζ, whereinThe alpha crystal form has relatively stable thermodynamic properties and is the only crystal form with application value in the formula of the solid propellant. However, currently α -AlH is to be substituted₃The solid propellant is applied to the solid propellant, and the decomposition phenomenon existing in the range of room temperature and the process temperature of the solid propellant needs to be solved.

C₆₀Can be used as an additive of a solid propellant, and can release additional tension energy and binding energy when the carbon cage structure is broken. Based on the method, the invention designs and synthesizes alpha-AlH₃/Al₂O₃/C₆₀Double shell structure of composite in which C is present₆₀The content is less than 1 percent, but the alpha-AlH can be obviously improved₃Thermal stability, contributing to propulsion of alpha-AlH₃Research on the practical application of the solid propellant.

Disclosure of Invention

In order to further improve the alpha-AlH based on acid pickling passivation₃The invention provides an alpha-AlH₃/Al₂O₃/C₆₀A double-shell structure compound, a synthetic method and application.

To achieve the above object, the present invention is realized by:

alpha-AlH₃/Al₂O₃/C₆₀The composite with the double-shell structure comprises an inner core, a first shell layer wrapping the inner core and a second shell layer wrapping the first shell layer from inside to outside;

the kernel is alpha-AlH₃A core, the first shell layer is Al₂O₃Layer, the second shell layer is modified C₆₀A layer;

modification C₆₀Layer is C₆₀A material layer formed by carrying carboxyl.

Optionally, the diameter of the inner core is 200 nm-40 um;

the thickness of the first shell layer is 5-30 nm;

the thickness of the second shell layer is 1-15 nm.

Optionally, alpha-AlH₃/Al₂O₃/C₆₀Preparation method of double-shell structure compoundThe method comprises the following steps:

cleaning alpha-AlH with dilute hydrochloric acid solution₃Obtaining alpha-AlH₃/Al₂O₃Core/shell materials of construction, alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀Stirring and dispersing in a toluene/tetrahydrofuran mixed solvent to obtain the alpha-AlH₃/Al₂O₃/C₆₀A double shell structured composite.

Optionally, the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min.

Optionally, alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀The mass ratio of (A) to (B) is 5: 1; the volume ratio of toluene to tetrahydrofuran in the toluene/tetrahydrofuran mixed solvent is 2; the stirring and dispersing time is 4-12 h.

Optionally, said modification C₆₀The preparation method comprises the following steps:

collecting 170mg of 4-carboxybenzaldehyde and 150mg of C₆₀And 90mg sarcosine in turn in 50ml chlorobenzene; refluxing the chlorobenzene solution at 135 ℃ for 16h under nitrogen atmosphere; the solvent component in the product was removed by rotary evaporation to obtain a dark brown powder, which was then dispersed in a toluene/tetrahydrofuran mixed solvent (v/v ═ 2), and separated by silica gel column chromatography to obtain brown modified C₆₀And (3) sampling.

alpha-AlH₃/Al₂O₃/C₆₀The method for synthesizing the double-shell structure compound comprises the following steps:

cleaning alpha-AlH with dilute hydrochloric acid solution₃Obtaining alpha-AlH₃/Al₂O₃Core/shell materials of construction, alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀Stirring and dispersing in a toluene/tetrahydrofuran mixed solvent to obtain the alpha-AlH₃/Al₂O₃/C₆₀A double shell structured composite.

Optionally, the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min;

α-AlH₃/Al₂O₃core/shell structure material and modified C₆₀The mass ratio of (A) to (B) is 5: 1; the volume ratio of toluene to tetrahydrofuran in the toluene/tetrahydrofuran mixed solvent is 2; the stirring and dispersing time is 4-12 h.

Optionally, said modification C₆₀The preparation method comprises the following steps:

collecting 170mg of 4-carboxybenzaldehyde and 150mg of C₆₀And 90mg sarcosine in turn in 50ml chlorobenzene; refluxing the chlorobenzene solution at 135 ℃ for 16h under nitrogen atmosphere; the solvent component in the product was removed by rotary evaporation to obtain a dark brown powder, which was then dispersed in a toluene/tetrahydrofuran mixed solvent (v/v ═ 2), and separated by silica gel column chromatography to obtain brown modified C₆₀And (3) sampling.

The alpha-AlH of the invention₃/Al₂O₃/C₆₀Use of a double shell structure composite for the preparation of a solid propellant fuel.

The invention has the advantages and positive effects that:

alpha-AlH of the invention₃/Al₂O₃/C₆₀The double-shell structure compound realizes the further promotion of alpha-AlH on the basis of the acid pickling treatment method₃Purpose of thermal stability, alpha-AlH obtained by synthesis₃/Al₂O₃/C₆₀The double-shell structure compound can be used as a solid propellant fuel, the preparation process of the double-shell structure is carried out at normal temperature, and the preparation method is safe and reliable and is suitable for large-scale production.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:

FIG. 1 shows modification C obtained in example 1₆₀(ii) an infrared spectrum;

FIG. 2 shows α -AlH prepared in example 1₃/Al₂O₃/C₆₀TEM image of double-shell structure compound with Al in the middle of two dotted lines₂O₃Layer of C in the red circle₆₀A molecule;

FIG. 3. alpha. -AlH of example 1₃/Al₂O₃/C₆₀Thermal stability curve of the double shell structure composite at 60 ℃;

FIG. 4 is example 1. alpha. -AlH₃/Al₂O₃/C₆₀Thermal stability curves (different hydrochloric acid concentrations versus washing time) of the double shell structure composites at 60 ℃;

FIG. 5 is a view of alpha-AlH₃/Al₂O₃With alpha-AlH₃/Al₂O₃/C₆₀XRD pattern of the double-shell structure compound.

Detailed Description

The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

alpha-AlH of the invention₃/Al₂O₃/C₆₀Double shell structure compound: the inner core is alpha-AlH₃The first shell layer on the surface is Al₂O₃Layer, the second shell layer is modified C₆₀Layer, modification C₆₀Molecular attachment to Al₂O₃Layer surface, the thickness of the layer can be quantified by TEM characterization (see fig. 1); to C₆₀The purpose of the modification is to make C₆₀A large number of carboxyl groups are carried on the molecule, so that the Al is more easily attached to the Al₂O₃The surface of the layer. The compound comprises an inner core, a first shell layer wrapping the inner core and a second shell layer wrapping the first shell layer; the inner core is alpha-AlH₃A core with a first shell layer of Al₂O₃Layer, the second shell layer is modified C₆₀A layer; modification C₆₀Layer is at C₆₀Carrying a carboxyl group thereon. The diameter of the inner core is 200 nm-40 um; the thickness of the first shell layer is 5-30 nm; the thickness of the second shell layer is 1-15 nm. The composite material with the structure promotes alpha-AlH₃And (3) thermal stability.

The preparation method comprises the following steps:

the microstructure is shown in fig. 2. The synthesis process comprises the following steps: (1) from fullerene (C)₆₀) Preparation methodSex C₆₀(ii) a (2) Modification C₆₀With alpha-AlH₃Preparation of alpha-AlH₃/Al₂O₃/C₆₀A double shell structure compound;

cleaning alpha-AlH with dilute hydrochloric acid solution₃Obtaining alpha-AlH₃/Al₂O₃Core/shell materials of construction, alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀Stirring and dispersing in a toluene/tetrahydrofuran mixed solvent to obtain the alpha-AlH₃/Al₂O₃/C₆₀A double shell structured composite.

For example, the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min.

For example, alpha-AlH₃/Al₂O₃Core/shell structure material and modified C₆₀The mass ratio of (A) to (B) is 5: 1; the volume ratio of toluene to tetrahydrofuran in the toluene/tetrahydrofuran mixed solvent is 2; the stirring and dispersing time is 4-12 h.

Modification C₆₀The preparation method comprises the following steps:

collecting 170mg of 4-carboxybenzaldehyde and 150mg of C₆₀And 90mg sarcosine in turn in 50ml chlorobenzene; refluxing the chlorobenzene solution at 135 ℃ for 16h under nitrogen atmosphere; the solvent component in the product was removed by rotary evaporation to obtain a dark brown powder, which was then dispersed in a toluene/tetrahydrofuran mixed solvent (v/v ═ 2), and separated by silica gel column chromatography to obtain brown modified C₆₀And (3) sampling.

With alpha-AlH₃By contrast, the alpha-AlH synthesized by the method₃/Al₂O₃/C₆₀The thermal stability of the compound with a double-shell structure is obviously improved, and C in the compound structure₆₀The content is less than 1%. alpha-AlH of the invention₃/Al₂O₃/C₆₀The double-shell structure compound realizes the further promotion of alpha-AlH on the basis of the acid pickling treatment method₃Purpose of thermal stability, alpha-AlH obtained by synthesis₃/Al₂O₃/C₆₀The double-shell structure compound can be used as solid propellant fuel, the preparation process of the double-shell structure is carried out at normal temperature, and the preparation method is safe, reliable and suitable forFor large-scale production.