CN112919997B - graphene-Schiff base energetic MOFs and preparation method thereof - Google Patents
graphene-Schiff base energetic MOFs and preparation method thereof Download PDFInfo
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Abstract
The invention provides graphene-Schiff base energetic MOFs and a preparation method thereof, wherein a graphene-Schiff base metal complex is ultrasonically dispersed in a methanol solution, a 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex is dissolved in DMF, the two solutions are stirred and mixed, the mixed solution is placed in a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle and reacts for 48-60 hours at 180-200 ℃, and the graphene-Schiff base energetic MOFs is obtained through cooling, centrifuging, washing, freezing and drying. According to the invention, the excellent combustion catalytic performance of the graphene-Schiff base metal complex is ensured, and the stability of the organic metal complex is improved by anchoring on the surface of the graphene. In addition, the introduction of the energy-containing MOFs enables the catalyst to be energetic, can meet the requirement of weaponry on the energy characteristics of the solid propellant, and has excellent application prospect in the field of the solid propellant.
Description
Technical Field
The invention belongs to the field of solid propellants, relates to a combustion catalyst, and particularly relates to graphene-Schiff base energetic MOFs and a preparation method thereof.
Background
Solid propellants are a power source for tactical missiles and rocket weapons, and the performance of the solid propellants directly affects the precise striking, high-energy damage and viability of modern weaponry. With the development of weaponry, the energy demand on solid propellants has increased, and the replacement of inert materials with energetic materials has been a trend in the development of solid propellants.
The combustion catalyst is an important component of the solid propellant and plays an important role in adjusting the combustion performance of the solid propellant. The iron-copper compound catalyst system is usually used in a composite propellant with Ammonium Perchlorate (AP) as an oxidant, the lead-copper-carbon compound system is a common combustion catalyst in a double-base propellant, and the combustion speed of the double-base propellant can be further improved by introducing metal powder such as nickel and the like.
The Schiff base ligand is proved to have excellent catalytic activity on the solid propellant, and the positive synergistic catalytic action with the metal also enables the Schiff base metal complex to show better application potential in the field of solid propellant combustion catalysis. However, as an organometallic complex, schiff base metal complexes cause problems with compatibility and stability, and as an inert catalyst, also cause a reduction in the energy density of the propellant.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide graphene-Schiff base energetic MOFs and a preparation method thereof, and solve the technical problem that the energy level and the combustion stability of a combustion catalyst to a solid propellant need to be further improved on the basis of ensuring the combustion catalytic performance of the combustion catalyst in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the graphene-Schiff base energetic MOFs has a structural formula as follows:
in the formula:
M1mg, Co, Cu, Ni, Fe, Mn or Pb;
M2mg, Co, Cu, Ni, Fe, Mn or Pb;
Preferably, n is 0 to 4.
Preferably, M is1And M2The same or different.
The invention also provides a preparation method of the graphene-Schiff base energetic MOFs, which comprises the steps of ultrasonically dispersing the graphene-Schiff base metal complex in a methanol solution, dissolving the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex in DMF, stirring and mixing the two solutions, placing the mixed solution in a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, reacting for 48-60 hours at 180-200 ℃, cooling, centrifuging, washing, freezing and drying to obtain the graphene-Schiff base energetic MOFs.
Specifically, the graphene-schiff base energetic MOFs prepared by the method is the graphene-schiff base energetic MOFs.
Specifically, the mass ratio of the graphene-Schiff base metal complex to the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex is (0.1-10) to 1;
the volume ratio of DMF to methanol is 1 (1-5).
Preferably, the mass ratio of the graphene-Schiff base metal complex to the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex is 0.5: 1; the volume ratio of DMF to methanol was 1: 3.
Specifically, the preparation process of the graphene-schiff base metal complex comprises the following steps:
step one, preparing aminated graphene oxide:
dissolving aminosilane in absolute ethyl alcohol, dropwise adding the aminosilane into the graphene oxide ethanol dispersion liquid, reacting the aminosilane and the graphene oxide ethanol dispersion liquid at 78-85 ℃ for 2-4 hours, and cooling, washing and freeze-drying to obtain aminated graphene oxide;
wherein the mass ratio of aminosilane to graphene oxide is (5-15) to 1;
step two, preparing the graphene-Schiff base metal complex:
ultrasonically dispersing the aminated graphene oxide prepared in the first step in absolute ethyl alcohol, dissolving aldehyde in an absolute ethyl alcohol solution, dropwise adding the aldehyde into the aminated graphene oxide ethanol dispersion liquid, reacting the aminated graphene oxide with the aldehyde at 78-85 ℃ for 2-6 hours, cooling, washing, and freeze-drying to obtain a graphene-Schiff base complex;
weighing graphene-Schiff base complexes, ultrasonically dispersing the graphene-Schiff base complexes in absolute ethyl alcohol, dropwise adding a prepared first metal salt aqueous solution, reacting for 4-12 hours at 50-65 ℃, cooling, washing, and freeze-drying to obtain the graphene-Schiff base metal complexes;
wherein:
the mass ratio of aldehyde to aminated graphene oxide is (5-15) to 1;
the mass ratio of the first metal salt to the graphene-Schiff base complex is (2-5) to 1;
the volume ratio of the absolute ethyl alcohol to the water is (2-5) to 1;
the first metal salt is Mg salt, Co salt, Cu salt, Ni salt, Fe salt, Mn salt or Pb salt.
Specifically, the preparation process of the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex comprises the following steps:
dissolving 1,1 '-dihydroxy-5, 5' -bitetrazole dihydroxylamine salt in sulfuric acid water solution, heating and stirring until the solution is completely dissolved, cooling to room temperature to precipitate white crystals, filtering, washing with water, and freeze-drying to obtain 1,1 '-dihydroxy-5, 5' -bitetrazole;
dissolving 1,1 '-dihydroxy-5, 5' -bitetrazole in water, stirring at room temperature until the solution is completely dissolved, dropwise adding a second metal salt aqueous solution dissolved in water to generate a precipitate, continuously stirring for 30min, filtering, washing, and freeze-drying to obtain a 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex;
wherein the molar ratio of the 1,1 '-dihydroxy-5, 5' -bitetrazole to the metal ions in the second metal salt aqueous solution is (2-4): 1;
the second metal salt is Mg salt, Co salt, Cu salt, Ni salt, Fe salt, Mn salt or Pb salt.
Specifically, the method comprises the following steps:
step one, preparing aminated graphene oxide:
dissolving aminosilane in absolute ethyl alcohol, dropwise adding the aminosilane into the graphene oxide ethanol dispersion liquid, reacting the aminosilane and the graphene oxide ethanol dispersion liquid at 78-85 ℃ for 2-4 hours, and cooling, washing and freeze-drying to obtain aminated graphene oxide;
wherein the mass ratio of aminosilane to graphene oxide is (5-15) to 1;
step two, preparing the graphene-Schiff base metal complex:
ultrasonically dispersing the aminated graphene oxide prepared in the first step in absolute ethyl alcohol, dissolving aldehyde in an absolute ethyl alcohol solution, dropwise adding the aldehyde into the aminated graphene oxide ethanol dispersion liquid, reacting the aminated graphene oxide with the aldehyde at 78-85 ℃ for 2-6 hours, cooling, washing, and freeze-drying to obtain a graphene-Schiff base complex;
weighing graphene-Schiff base complexes, ultrasonically dispersing the graphene-Schiff base complexes in absolute ethyl alcohol, dropwise adding a prepared first metal salt aqueous solution, reacting for 4-12 hours at 50-65 ℃, cooling, washing, and freeze-drying to obtain the graphene-Schiff base metal complexes;
wherein:
the mass ratio of aldehyde to aminated graphene oxide is (5-15) to 1;
the mass ratio of the first metal salt to the graphene-Schiff base complex is (2-5) to 1;
the volume ratio of the absolute ethyl alcohol to the water is (2-5) to 1;
the first metal salt is Mg salt, Co salt, Cu salt, Ni salt, Fe salt, Mn salt or Pb salt;
step three, preparing the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex:
dissolving 1,1 '-dihydroxy-5, 5' -bitetrazole dihydroxylamine salt in sulfuric acid water solution, heating and stirring until the solution is completely dissolved, cooling to room temperature to precipitate white crystals, filtering, washing with water, and freeze-drying to obtain 1,1 '-dihydroxy-5, 5' -bitetrazole;
dissolving 1,1 '-dihydroxy-5, 5' -bitetrazole in water, stirring at room temperature until the solution is completely dissolved, dropwise adding a second metal salt aqueous solution dissolved in water to generate a precipitate, continuously stirring for 30min, filtering, washing, and freeze-drying to obtain a 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex;
wherein the molar ratio of the 1,1 '-dihydroxy-5, 5' -bitetrazole to the metal ions in the second metal salt aqueous solution is (2-4): 1;
the second metal salt is Mg salt, Co salt, Cu salt, Ni salt, Fe salt, Mn salt or Pb salt.
Step four, preparing the graphene-Schiff base energetic MOFs:
ultrasonically dispersing the graphene-Schiff base metal complex prepared in the second step into a methanol solution, dissolving the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex prepared in the third step into DMF, stirring and mixing the two solutions, placing the mixed solution into a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, reacting for 48-60 h at 180-200 ℃, cooling, centrifuging, washing, freezing and drying to obtain the graphene-Schiff base energetic MOFs.
Preferably, the aminosilane is KH-550, KH-590 or KH-792.
Compared with the prior art, the invention has the following technical effects:
according to the invention, (I) the excellent combustion catalytic performance of the graphene-Schiff base metal complex is guaranteed, and the stability of the organic metal complex is improved by anchoring on the surface of the graphene. In addition, the introduction of the energy-containing MOFs enables the catalyst to be energetic, can meet the requirement of weaponry on the energy characteristics of the solid propellant, and has excellent application prospect in the field of the solid propellant.
The graphene-Schiff base energetic MOFs realizes the assembly of a catalytic active substance graphene-Schiff base metal complex and the energetic MOFs on a molecular level, and endows the graphene-Schiff base metal complex with an energy characteristic on the basis of excellent combustion catalytic performance so as to meet the requirement of weapon equipment development on the energy characteristic of a solid propellant, and the graphene-Schiff base energetic MOFs can be used as a functional energetic combustion catalyst.
(III) the S-NGO-EMOFs prepared by the method can activate the catalytic active material graphene-Schiff base metal complex in an energy-containing manner, and can be used as a functional energy-containing combustion catalyst in a solid propellant.
Drawings
FIG. 1 is an EDS spectrum of S-NGO-EMOFs-Fe of example 1.
FIG. 2 is the EDS spectrum of S-NGO-EMOFs-Cu) of example 2.
FIG. 3 is the EDS spectrum of S-NGO-EMOFs-Ni) of example 3.
FIG. 4 is the EDS spectrum of S-NGO-EMOFs-Co/Ni of example 5.
FIG. 5 is an FTIR spectrum of S-NGO-EMOFs of examples 1 to 5.
FIG. 6 is a DTG spectrum of S-NGO-EMOFs of examples 1 to 5.
FIG. 7 is a DSC curve of AP before and after mixing of S-NGO-EMOFs-Fe or Cu) of example 1 or 2.
FIG. 8 is a DSC curve of AP before and after S-NGO-EMOFs-Ni/Co or Co/Ni) blending of example 4 or example 5.
The details of the present invention will be described in further detail below with reference to the accompanying drawings and examples.
Detailed Description
In the present invention, it is to be noted that:
MOFs are short for Metal organic Framework compounds (English name Metal organic Framework).
NGO is short for aminated graphene oxide.
S-NGO is short for graphene-Schiff base complex.
S-NGO-M1Is a abbreviation of graphene-Schiff base metal complex, M1Mg, Co, Cu, Ni, Fe, Mn or Pb.
S-NGO-EMOFs are short for graphene-Schiff base energetic MOFs.
TKX-50 is an abbreviation for 1,1 '-dihydroxy-5, 5' -bitetrazole diamine salt.
BTO is an abbreviation for 1,1 '-dihydroxy-5, 5' -bitetrazole.
BTO-M2Is abbreviation of 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex, M2Mg, Co, Cu, Ni, Fe, Mn or Pb.
DMF is N, N-dimethylformamide for short.
The graphene oxide used in the present invention is a known commercially available product, and preferably, the carbon-oxygen molar ratio of the graphene oxide is 1: 1.
Preferably, the aminosilane used in the present invention is available under the trade name KH-550, KH-590 or KH-792.
In the invention, the preparation process of BTO comprises the following steps: dissolving 1,1 '-dihydroxy-5, 5' -bistetrazole dihydroxylamine (TKX-50) 5g in 50% sulfuric acid water solution 60g at 90 deg.C, heating and stirring to dissolve completely, cooling to room temperature to precipitate white crystal, filtering, washing with water, and freeze drying to obtain 1,1 '-dihydroxy-5, 5' -Bistetrazole (BTO).
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of graphene-schiff base energetic MOFs, which comprises the following steps:
step one, preparing aminated graphene oxide:
dissolving 30g of aminosilane KH-550 in a proper amount of absolute ethyl alcohol, and dropwise adding the aminosilane KH-550 into the graphene oxide ethanol dispersion liquid, wherein the concentration of graphene oxide is 2g and 2 g.L-1And reacting the two at 80 ℃ for 2h, cooling, washing, freezing and drying to obtain the aminated graphene oxide (NGO).
Step two, preparing the graphene-Schiff base metal complex:
ultrasonically dispersing 2g of aminated graphene oxide (NGO) prepared in the first step into absolute ethyl alcohol, dissolving 30g of salicylaldehyde into the absolute ethyl alcohol solution, dropwise adding the salicylaldehyde into the aminated graphene oxide ethanol dispersion liquid, reacting the two solutions at 80 ℃ for 3 hours, cooling, washing, and freeze-drying to obtain the graphene-Schiff base complex (S-NGO).
Weighing 2g of graphene-Schiff base complex, ultrasonically dispersing in 1L of absolute ethyl alcohol, dissolving 4g of ferrous chloride tetrahydrate in 500mL of water, dropwise adding the prepared ferrous chloride tetrahydrate aqueous solution, reacting at 65 ℃ for 6h, cooling, washing, and freeze-drying to obtain the graphene-Schiff base iron complex (S-NGO-Fe).
Step three, preparing the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex:
dissolving 1,1 '-dihydroxy-5, 5' -Bitetrazole (BTO) 1.63g in water 50mL, stirring at room temperature until the solution is completely dissolved, adding ferrous chloride tetrahydrate aqueous solution 30mL dropwise, wherein the solute is ferrous chloride tetrahydrate 1.90g, generating light yellow precipitate, continuously stirring for 30min, filtering, washing, and freeze-drying to obtain the iron complex of 1,1 '-dihydroxy-5, 5' -bitetrazole (BTO-Fe).
Step four, preparing the graphene-Schiff base energetic MOFs:
and ultrasonically dispersing 90mg of the graphene-Schiff base iron complex (S-NGO-Fe) prepared in the second step into 45ml of methanol solution, dissolving 180mg of the 1,1 '-dihydroxy-5, 5' -bitetrazole iron complex (BTO-Fe) prepared in the third step into 15ml of DMMF, stirring and mixing the two solutions, putting the mixed solution into a polytetrafluoroethylene lining of a 100ml stainless steel high-pressure reaction kettle, reacting for 48 hours at 180 ℃, cooling, centrifuging, washing, freezing and drying to obtain the graphene-Schiff base energetic MOFs (S-NGO-EMOFs-Fe).
The structural formula of the S-NGO-EMOFs-Fe prepared in the embodiment is as follows:
in the formula:
M1＝Fe；M2＝Fe；
in the present embodiment, the first and second electrodes are,
means that 2 can be connected
A group.
The S-NGO-EMOFs-Fe prepared by the embodiment reserves the better dispersion property of the graphene-based material, and the uniformly distributed active Fe can be used as a catalytic active site to effectively promote AP thermal decomposition and AP-based propellant combustion. Compared with the ferrocene burning-rate catalyst applied to the current AP-based propellant, the ferrocene burning-rate catalyst not only effectively improves the characteristics of easy volatilization and migration of ferrocene and derivatives thereof, but also endows the solid propellant with the characteristic of high-energy insensitivity besides keeping better catalytic performance compared with inert catalysts such as ferrocene and derivatives thereof, graphene-Schiff base iron complexes and the like, is beneficial to the improvement of the energy and the specific impulse of the solid propellant, and is an important development direction of the combustion catalyst.
Example 2:
the embodiment provides a preparation method of graphene-schiff base energetic MOFs, which comprises the following steps:
step one, preparing aminated graphene oxide:
30g of aminosilane KH-792 is dissolved in a proper amount of absolute ethyl alcohol and is dropwise added into the graphene oxide ethanol dispersion liquid, wherein the graphene oxide is 2g, and the concentration is 2 g.L-1And reacting the two at 80 ℃ for 2h, cooling, washing, freezing and drying to obtain the aminated graphene oxide (NGO).
Step two, preparing the graphene-Schiff base metal complex:
ultrasonically dispersing 2g of aminated graphene oxide (NGO) prepared in the first step into absolute ethyl alcohol, dissolving 20g of salicylaldehyde into the absolute ethyl alcohol solution, dropwise adding the salicylaldehyde into the aminated graphene oxide ethanol dispersion liquid, reacting the two solutions at 80 ℃ for 3 hours, cooling, washing, and freeze-drying to obtain the graphene-Schiff base complex (S-NGO).
Weighing 2g of graphene-Schiff base complex, ultrasonically dispersing in 1L of absolute ethyl alcohol, dissolving 4g of copper nitrate trihydrate in 500mL of water, dropwise adding the prepared copper nitrate trihydrate aqueous solution, reacting for 6h at 65 ℃, cooling, washing, and freeze-drying to obtain the graphene-Schiff base copper complex (S-NGO-Cu).
Step three, preparing the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex:
dissolving 1,1 '-dihydroxy-5, 5' -Bitetrazole (BTO) 1.6g in water 80mL, stirring at room temperature until the solution is completely dissolved, adding copper nitrate trihydrate 20mL dropwise, wherein the solute is 2.314g of copper nitrate trihydrate to generate green precipitate, continuously stirring for 30min, filtering, washing, and freeze-drying to obtain copper 1,1 '-dihydroxy-5, 5' -bitetrazole complex (BTO-Cu).
Step four, preparing the graphene-Schiff base energetic MOFs:
and ultrasonically dispersing 90mg of the graphene-Schiff base copper complex (S-NGO-Cu) prepared in the second step into 45mL of methanol solution, dissolving 180mg of the 1,1 '-dihydroxy-5, 5' -bitetrazole copper complex (BTO-Cu) prepared in the third step into 15mL of DMF, stirring and mixing the two solutions, putting the mixed solution into a polytetrafluoroethylene lining of a 100mL stainless steel high-pressure reaction kettle, reacting for 48 hours at 180 ℃, cooling, centrifuging, washing, freezing and drying to obtain the graphene-Schiff base energetic MOFs (S-NGO-EMOFs-Cu).
The structural formula of (S-NGO-EMOFs-Cu) prepared in this example is substantially the same as that of example 1 except that: m1＝Cu；M2＝Cu。
The S-NGO-EMOFs-Cu prepared by the embodiment reserves the better dispersion property of the graphene-based material, and the uniformly distributed active Cu can be used as a catalytic active site and can be used as a combustion catalyst of a composite and modified dual-system propellant. Compared with the currently applied inert combustion catalyst, the S-NGO-EMOFs-Cu has better catalytic performance, and the introduction of the graphene-based material and the energy-containing MOFs endows the solid propellant with the characteristic of high-energy insensitivity, contributes to the improvement of the energy and specific impulse of the solid propellant, and is an important development direction of the combustion catalyst.
Example 3:
the embodiment provides a preparation method of graphene-schiff base energetic MOFs, which comprises the following steps:
step one, preparing aminated graphene oxide:
dissolving 30g of aminosilane KH-590 in a proper amount of absolute ethyl alcohol, and dropwise adding the aminosilane KH-590 into the graphene oxide ethanol dispersion liquid, wherein the graphene oxide is 2g, and the concentration is 2 g.L-1Reacting the two at 80 ℃ for 2h, cooling, washing, and freeze-drying to obtain the final productTo aminated graphene oxide (NGO).
Step two, preparing the graphene-Schiff base metal complex:
ultrasonically dispersing 2g of aminated graphene oxide (NGO) prepared in the first step into absolute ethyl alcohol, dissolving 30g of salicylaldehyde into the absolute ethyl alcohol solution, dropwise adding the salicylaldehyde into the aminated graphene oxide ethanol dispersion liquid, reacting the two solutions at 80 ℃ for 3 hours, cooling, washing, and freeze-drying to obtain the graphene-Schiff base complex (S-NGO).
Weighing 2g of graphene-Schiff base complex, ultrasonically dispersing in 1L of absolute ethyl alcohol, dissolving 4g of nickel chloride hexahydrate in 500mL of water, dropwise adding the prepared nickel chloride hexahydrate aqueous solution, reacting for 6 hours at 65 ℃, cooling, washing, and freeze-drying to obtain the graphene-Schiff base nickel complex (S-NGO-Ni).
Step three, preparing the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex:
the method comprises the steps of dissolving 1,1 '-dihydroxy-5, 5' -Bitetrazole (BTO) 2g in water 90mL, stirring at room temperature until the solution is completely dissolved, then dropwise adding nickel chloride hexahydrate 30mL, wherein the solute is nickel chloride hexahydrate 3.41g, generating light blue precipitate, continuously stirring for 30min, filtering, washing, and freeze-drying to obtain the 1,1 '-dihydroxy-5, 5' -bitetrazole nickel complex (BTO-Ni).
Step four, preparing the graphene-Schiff base energetic MOFs:
and ultrasonically dispersing 90mg of the graphene-Schiff base nickel complex (S-NGO-Ni) prepared in the second step into 45mL of methanol solution, dissolving 180mg of the 1,1 '-dihydroxy-5, 5' -bitetrazole nickel complex (BTO-Ni) prepared in the third step into 15mL of DMF, stirring and mixing the two solutions, putting the mixed solution into a polytetrafluoroethylene lining of a 100mL stainless steel high-pressure reaction kettle, reacting for 48 hours at 180 ℃, cooling, centrifuging, washing, freezing and drying to obtain the graphene-Schiff base energetic MOFs (S-NGO-EMOFs-Ni).
The structural formula of the S-NGO-EMOFs-Ni prepared in the embodiment is as follows:
in the formula: m1＝Ni；M2＝Ni；
In the present embodiment, the first and second electrodes are,
means that 2 can be connected
A group.
The S-NGO-EMOFs-Ni prepared by the embodiment can be used as a functional combustion aid to be used in a double-base solid propellant, compared with the currently added metal nickel powder, the burning rate of the propellant can be effectively improved, and the introduced graphene material is beneficial to the sensitivity and reduction of the solid propellant and the improvement of the mechanical property. In addition, compared with the addition of the inert nickel powder, the energetic MOFs can reduce the influence of the reduction of the energy and specific impulse of the solid propellant caused by the addition of the inert material, and can endow the solid propellant with more efficacy performance.
Example 4:
the embodiment provides a preparation method of graphene-schiff base energetic MOFs, which comprises the following steps:
step one, preparing aminated graphene oxide:
same as in step 1 of example 3.
Step two, preparing the graphene-Schiff base metal complex:
the graphene-schiff base nickel complex (S-NGO-Ni) was obtained in the same manner as in the second step of example 3.
Step three, preparing the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex:
dissolving 2g of 1,1 '-dihydroxy-5, 5' -Bitetrazole (BTO) in 60mL of water, stirring at room temperature until the solution is completely dissolved, dropwise adding 15mL of cobalt nitrate hexahydrate aqueous solution, wherein the solute is 3.4g of cobalt nitrate hexahydrate to generate light pink precipitate, continuously stirring for 30min, filtering, washing, and freeze-drying to obtain the 1,1 '-dihydroxy-5, 5' -bitetrazole cobalt complex (BTO-Co).
Step four, preparing the graphene-Schiff base energetic MOFs:
and ultrasonically dispersing 90mg of the graphene-Schiff base nickel complex (S-NGO-Ni) prepared in the second step into 45mL of methanol solution, dissolving 180mg of the 1,1 '-dihydroxy-5, 5' -bitetrazole cobalt complex (BTO-Co) prepared in the third step into 15mL of DMF, stirring and mixing the two solutions, putting the mixed solution into a polytetrafluoroethylene lining of a 100mL stainless steel high-pressure reaction kettle, reacting for 48 hours at 180 ℃, cooling, centrifuging, washing, freezing and drying to obtain the graphene-Schiff base energetic MOFs (S-NGO-EMOFs-Ni/Co).
The structural formula of S-NGO-EMOFs-Ni/Co prepared in this example is substantially the same as that of example 3, except that: m1＝Ni；M2＝Co。
The S-NGO-EMOFs-Ni/Co prepared by the embodiment can be used as a functional combustion aid for composite or dual-base solid propellants, and compared with the currently added metal nickel powder, the coordination and combination of the S-NGO-EMOFs-Ni/Co in the same molecule enable the synergistic effect to be better than that of a physically mixed sample, and the catalytic performance is better and the stability is better. In addition, compared with the addition of the inert material, the energetic MOFs can reduce the influence of the reduction of the energy and specific impulse of the solid propellant caused by the addition of the inert material, and endow the solid propellant with more efficacy performance.
Example 5:
the embodiment provides a preparation method of graphene-schiff base energetic MOFs, which comprises the following steps:
step one, preparing aminated graphene oxide:
same as in step 1 of example 2.
Step two, preparing the graphene-Schiff base metal complex:
ultrasonically dispersing 2g of aminated graphene oxide (NGO) prepared in the first step into absolute ethyl alcohol, dissolving 30g of salicylaldehyde into the absolute ethyl alcohol solution, dropwise adding the salicylaldehyde into the aminated graphene oxide ethanol dispersion liquid, reacting the two solutions at 80 ℃ for 3 hours, cooling, washing, and freeze-drying to obtain the graphene-Schiff base complex (S-NGO).
Weighing 2g of graphene-Schiff base complex, ultrasonically dispersing in 1L of absolute ethyl alcohol, dissolving 4g of copper nitrate trihydrate in 500mL of water, dropwise adding the prepared copper nitrate aqueous solution, reacting for 6h at 65 ℃, cooling, washing, and freeze-drying to obtain the graphene-Schiff base copper complex (S-NGO-Cu).
Step three, preparing the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex:
in the same manner as in step three of example 3, iron complex of 1,1 '-dihydroxy-5, 5' -bitetrazole (BTO-Fe) was obtained.
Step four, preparing the graphene-Schiff base energetic MOFs:
and ultrasonically dispersing 90mg of the graphene-Schiff base copper complex (S-NGO-Cu) prepared in the second step into 45mL of methanol solution, dissolving 180mg of the 1,1 '-dihydroxy-5, 5' -bitetrazole iron complex (BTO-Ni) prepared in the third step into 15mL of DMF, stirring and mixing the two solutions, putting the mixed solution into a polytetrafluoroethylene lining of a 100mL stainless steel high-pressure reaction kettle, reacting for 48 hours at 180 ℃, cooling, centrifuging, washing, freezing and drying to obtain the graphene-Schiff base energetic MOFs (S-NGO-EMOFs-Cu/Fe).
The structural formula of S-NGO-EMOFs-Cu/Fe obtained in this example is substantially the same as that of example 2, except that: m1＝Cu；M2＝Fe。
The S-NGO-EMOFs-Cu/Fe prepared by the embodiment reserves the better dispersion property of the graphene-based material, and the uniformly distributed active Fe and Cu can be used as catalytic active sites to synergistically catalyze the AP thermal decomposition and the AP-based propellant combustion. Compared with burning rate catalysts, namely the carbetocin and the copper chromite, applied in the existing composite propellant, the composite propellant not only effectively improves the characteristics of easy volatilization and migration of the carbetocin, but also has better synergistic catalytic effect compared with a physically mixed catalyst. In addition, the use of the graphene-based energetic MOFs endows the solid propellant with the characteristic of high-energy insensitivity, and contributes to the improvement of the energy and the specific impulse of the solid propellant.
Following the technical solution in the above embodiment, fig. 1 to 8 are obtained.
FIG. 1 is an EDS spectrum of S-NGO-EMOFs-Fe of example 1. As can be seen from FIG. 1, the S-NGO-EMOFs-Fe retains the better two-dimensional structure of the graphene material, and the result shows that C, O, N, Fe elements exist, so that the successful preparation of the S-NGO-EMOFs-Fe is confirmed.
FIG. 2 is the EDS spectrum of S-NGO-EMOFs-Ni) of example 2. As can be seen from FIG. 2, the S-NGO-EMOFs-Ni retains the better two-dimensional structure of the graphene material, and the result shows that C, O, N, Ni elements exist, thereby confirming the successful preparation of the S-NGO-EMOFs-Ni.
FIG. 3 is the EDS spectrum of S-NGO-EMOFs-Cu) of example 3. As can be seen from FIG. 3, the S-NGO-EMOFs-Cu retains the better two-dimensional structure of the graphene material, and the result shows that C, O, N, Cu elements exist, thereby confirming the successful preparation of the S-NGO-EMOFs-Cu.
FIG. 4 is the EDS spectrum of S-NGO-EMOFs-Co/Ni of example 5. As can be seen from FIG. 4, the S-NGO-EMOFs-Co/Ni retains the better two-dimensional structure of the graphene material, and the results show the existence of C, O, Co and Ni elements, thereby confirming the successful preparation of the S-NGO-EMOFs-Co/Ni.
FIG. 5 is an FTIR spectrum of S-NGO-EMOFs of examples 1 to 5. As can be seen from fig. 5, the peak of vibration of the carboxyl group was significantly reduced, indicating that the carboxyl group was bound as a site to the coupling agent, and the occurrence of the peak of EMOFs confirms the successful preparation of S-NGO-EMOFs.
FIG. 6 is a DTG spectrum of S-NGO-EMOFs of examples 1 to 5. As can be seen from FIG. 6, the five prepared NGO-EMOFs materials have good thermal stability, and the peak temperature of DTG is above 300 ℃.
FIG. 7 is a DSC curve of AP before and after mixing of S-NGO-EMOFs-Fe and Cu of examples 1 and 2. As can be seen from FIG. 7, the prepared S-NGO-EMOFs-Fe and Cu can effectively promote the thermal decomposition of AP, so that the peak temperature of the high-temperature decomposition of AP is remarkably reduced, and the prepared S-NGO-EMOFs-Fe can be used as a combustion catalyst of an AP-based propellant.
FIG. 8 is a DSC plot of AP before and after mixing of S-NGO-EMOFs-Ni/Co and Co/Ni) of examples 4 and 5. As can be seen from FIG. 8, the prepared S-NGO-EMOFs-Ni/Co and Co/Ni can effectively promote the thermal decomposition of AP, so that the peak temperature of the high-temperature decomposition of AP is remarkably reduced, and the catalyst can be used as a combustion catalyst of an AP-based propellant.
Example 6:
this example shows a preparation method of graphene-schiff base energetic MOFs, which is basically the same as example 1 except that the first metal salt and the second metal salt are replaced from ferrous chloride tetrahydrate of example 1 to magnesium nitrate hexahydrate of this example.
Example 7:
this example shows a preparation method of graphene-schiff base energetic MOFs, which is basically the same as example 1 except that the first metal salt and the second metal salt are replaced from ferrous chloride tetrahydrate of example 1 to manganese acetate of this example.
Example 8:
this example shows a preparation method of graphene-schiff base energetic MOFs, which is basically the same as example 1 except that the first metal salt and the second metal salt are replaced from ferrous chloride tetrahydrate of example 1 to lead nitrate of this example.
Claims (3)
1. A preparation method of graphene-Schiff base energetic MOFs is characterized by comprising the following steps:
step one, preparing aminated graphene oxide:
dissolving aminosilane in absolute ethyl alcohol, dropwise adding the aminosilane into the graphene oxide ethanol dispersion liquid, reacting the aminosilane and the graphene oxide ethanol dispersion liquid at 78-85 ℃ for 2-4 hours, and cooling, washing and freeze-drying to obtain aminated graphene oxide;
wherein the mass ratio of aminosilane to graphene oxide is (5-15) to 1;
step two, preparing the graphene-Schiff base metal complex:
ultrasonically dispersing the aminated graphene oxide prepared in the first step in absolute ethyl alcohol, dissolving aldehyde in an absolute ethyl alcohol solution, dropwise adding the aldehyde into the aminated graphene oxide ethanol dispersion liquid, reacting the aminated graphene oxide with the aldehyde at 78-85 ℃ for 2-6 hours, cooling, washing, and freeze-drying to obtain a graphene-Schiff base complex;
weighing graphene-Schiff base complexes, ultrasonically dispersing the graphene-Schiff base complexes in absolute ethyl alcohol, dropwise adding a prepared first metal salt aqueous solution, reacting for 4-12 hours at 50-65 ℃, cooling, washing, and freeze-drying to obtain the graphene-Schiff base metal complexes;
wherein:
the mass ratio of aldehyde to aminated graphene oxide is (5-15) to 1;
the mass ratio of the first metal salt to the graphene-Schiff base complex is (2-5) to 1;
the volume ratio of the absolute ethyl alcohol to the water is (2-5) to 1;
the first metal salt is Mg salt, Co salt, Cu salt, Ni salt, Fe salt, Mn salt or Pb salt;
step three, preparing the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex:
dissolving 1,1 '-dihydroxy-5, 5' -bitetrazole dihydroxylamine salt in sulfuric acid water solution, heating and stirring until the solution is completely dissolved, cooling to room temperature to precipitate white crystals, filtering, washing with water, and freeze-drying to obtain 1,1 '-dihydroxy-5, 5' -bitetrazole;
dissolving 1,1 '-dihydroxy-5, 5' -bitetrazole in water, stirring at room temperature until the solution is completely dissolved, dropwise adding a second metal salt aqueous solution dissolved in water to generate a precipitate, continuously stirring for 30min, filtering, washing, and freeze-drying to obtain a 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex;
wherein the molar ratio of the 1,1 '-dihydroxy-5, 5' -bitetrazole to the metal ions in the second metal salt aqueous solution is (2-4): 1;
the second metal salt is Mg salt, Co salt, Cu salt, Ni salt, Fe salt, Mn salt or Pb salt;
step four, preparing the graphene-Schiff base energetic MOFs:
ultrasonically dispersing the graphene-Schiff base metal complex prepared in the step two in a methanol solution, dissolving the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex prepared in the step three in DMF, stirring and mixing the two solutions, placing the mixed solution in a polytetrafluoroethylene lining of a stainless steel high-pressure reaction kettle, reacting for 48-60 h at 180-200 ℃, cooling, centrifuging, washing, freezing and drying to obtain graphene-Schiff base energetic MOFs;
the mass ratio of the graphene-Schiff base metal complex to the 1,1 '-dihydroxy-5, 5' -bitetrazole metal complex is 0.5: 1;
the volume ratio of DMF to methanol is 1: 3;
the structural formula of the graphene-Schiff base energetic MOFs prepared by the method is as follows:
or
In the formula:
M1mg, Co, Cu, Ni, Fe, Mn or Pb;
M2mg, Co, Cu, Ni, Fe, Mn or Pb;
2. The method for preparing the graphene-schiff base energetic MOFs according to claim 1, wherein M is1And M2The same or different.
3. The method for preparing the graphene-schiff base energetic MOFs according to claim 1, wherein the aminosilane is aminosilane KH-550, aminosilane KH-590 or aminosilane KH-792.
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