CN115744841B - Nickel-based nitride nano combustion catalyst and preparation method thereof - Google Patents
Nickel-based nitride nano combustion catalyst and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 39
- 238000005121 nitriding Methods 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003421 catalytic decomposition reaction Methods 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 5
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003380 propellant Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000004449 solid propellant Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000028 HMX Substances 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- -1 cobalt nitride Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
The invention discloses a nickel-based nitride nano combustion catalyst and a preparation method thereof, wherein the nickel-based nitride nano combustion catalyst comprises a Ni 3 N nano combustion catalyst, an O-doped Ni 3 N nano combustion catalyst and a molybdenum, vanadium or chromium-doped Ni 3 N nano combustion catalyst; the nickel-based nitride nano combustion catalyst is prepared by adopting a precursor of high-temperature nitriding NiO nano sheets, the NiO nano sheets are prepared by combining hydrothermal synthesis with a high-temperature annealing method, the adjustment of the oxygen-nitrogen ratio is realized by changing the nitriding temperature, and the bimetal structure is realized by introducing other transition metal precursors into a hydrothermal reaction solution. Compared with the traditional nickel oxide, the invention is favorable for improving the activity of the catalyst, can better match the energy level structure of HATO and realizes high-efficiency catalytic decomposition.
Description
Technical Field
The invention belongs to the field of solid propellants, relates to a combustion catalyst, and in particular relates to a nickel-based nitride nano combustion catalyst and a preparation method thereof.
Background
Improving safety is a necessary requirement for the development of solid propellant technology. The use of 5,5 '-bitetrazole-1, 1' -dioxydihydroxyamine salt (HATO) in place of either hexogen or octogen is an effective way to improve the safety of the propellant. However, the introduction of HATO significantly improves the safety performance of the propellant and also results in the deterioration of the combustion performance of the propellant, the combustion speed pressure index is greatly improved, and then the disassembly explosion occurs in the working process of the engine. This has become a key bottleneck limiting the practical implementation of such solid propellants.
The combustion catalyst is the most commonly used method for adjusting and improving the combustion performance of the propellant, and the combustion speed pressure index of the propellant can be controllably adjusted within a wider pressure range. However, as solid rocket propellants further evolve toward high energy, gas cleaning, and combustion control, the catalytic efficiency of existing combustion catalysts has been difficult to meet the requirements of high performance solid propellants, and there is a need to develop new combustion catalytic material systems with high activity and high selectivity.
In general, the catalytic activity of a combustion catalyst is related to its geometry and electronic structure, which involves activation of energetic molecules and adsorption of reaction intermediates that participate in catalytic reactions. For transition metals, the adsorption strength of intermediate species that are capable of molecular catalytic decomposition depends on the d-band center of the transition metal. Ni has a variable valence state, which allows Ni to regulate its electronic structure by coordinating with different electronegative elements such as carbon, nitrogen, oxygen, etc. Therefore, ni can be tuned to a highly active combustion catalytic active site by adjusting the d-band center of Ni to a reasonable position.
Changing the coordination environment of metals is an effective method for regulating and controlling the electronic structure of active metal centers. For energetic molecules, there is often a nitrogen element in the structure. Therefore, the introduction of nitrogen element into the catalyst can improve the adsorption capacity of the catalytic active center to the energetic molecules. On the basis, the d-band center position of Ni can be effectively regulated and controlled by regulating the oxygen-nitrogen ratio in the coordination atom, so that the catalytic activity of the catalyst is improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a nickel-based nitride nano combustion catalyst and a preparation method thereof, wherein the catalyst utilizes the energy difference between d energy bands of different transition metals and Ni and the influence of coordination environment on the d-band structure of Ni, and the valence band structure of the nickel-based nitride is moved by adjusting the nitrogen-oxygen ratio and the interface polarization effect, so that the performance of the metal nitride for combustion catalysis is regulated and controlled, and the efficient catalytic decomposition of typical energetic molecules such as HATO is realized.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the nickel-based nitride nano combustion catalyst comprises the following steps:
step 1, mixing raw materials of nickel salt, urea and NH 4 F for hydrothermal reaction, wherein the hydrothermal reaction temperature is 120 ℃, and the reaction time is 9 hours; cooling to room temperature, centrifuging, washing the centrifugal precipitate with deionized water and ethanol for three times, and drying in a vacuum oven at 60deg.C for more than 12 hr to obtain green powdery product;
Step 2, annealing the product obtained in the step1 in argon atmosphere for 2 hours to obtain a precursor;
and step 3, nitriding the precursor prepared in the step2 in an ammonia atmosphere to obtain the nickel-based nitride nano combustion catalyst.
The invention also comprises the following technical characteristics:
specifically, the nickel salt in the step1 is one of nickel nitrate, nickel acetate and nickel acetylacetonate.
Specifically, the molar ratio of the nickel salt to the urea to the NH 4 F is 1: (2-5): (1-3).
Specifically, the annealing temperature in the step2 is 300-650 ℃, and the argon flow rate is 100-300 mL/min.
Specifically, the nitriding temperature in the step 3 is 350-600 ℃, the nitriding time is 2h, the ammonia flow rate is 80-180 mL/min, and the nickel-based nitride nano combustion catalyst prepared at the moment is Ni 3 N nano combustion catalyst.
Specifically, the nitriding temperature in the step 3 is 350 ℃, the nitriding time is 1.5h, the ammonia flow rate is 80-180 mL/min, and the nickel-based nitride nano combustion catalyst prepared at the moment is an O-doped Ni 3 N nano combustion catalyst.
Specifically, in the step 1, the raw material of the hydrothermal reaction further includes a transition metal precursor, the transition metal precursor is one of molybdate, vanadate and chromate, and the nickel-based nitride nano combustion catalyst prepared according to the step of claim 2 is a molybdenum, vanadium or chromium doped Ni 3 N nano combustion catalyst.
Specifically, in the raw materials for the hydrothermal reaction in the step1, the molar ratio of the nickel salt, the transition metal precursor, urea and NH 4 F is 1:0.1: (2-5): (1-3).
Specifically, the annealing temperature in the step 2 is 300-650 ℃, and the argon flow rate is 100-300 mL/min; the nitriding temperature in the step 3 is 350-600 ℃, the nitriding time is 2h, and the ammonia flow rate is 80-180 mL/min.
The nickel-based nitride nano combustion catalyst is prepared by adopting the preparation method of the nickel-based nitride nano combustion catalyst.
Compared with the prior art, the invention has the following technical effects:
(1) According to the invention, the nickel oxide is subjected to high-temperature nitridation treatment to obtain the cobalt nitride, and compared with the traditional nickel oxide, the nitrogen has unpaired electrons which can provide more unoccupied d orbitals, so that the catalyst activity is improved.
(2) According to the invention, the effective regulation and control of d-orbit energy are realized by doping Ni 3 N, the energy level structure of HATO can be better matched, and high-efficiency catalytic decomposition is realized.
(3) The preparation method of the nickel-based nitride provided by the invention is simple, the raw materials are easy to obtain, the preparation is easy to amplify, and engineering application is facilitated.
Drawings
FIG. 1 is an electron micrograph and XRD pattern of Ni 3 N;
FIG. 2 is an electron micrograph and XRD pattern of O-doped Ni 3 N;
FIG. 3 is an electron micrograph and XRD pattern of Mo-doped Ni 3 N;
FIG. 4 is a DSC curve of a nickel-based nitride mixed with commercial nickel oxide HATO.
Detailed Description
The invention provides a nickel-based nitride nano combustion catalyst and a preparation method thereof, wherein the nickel-based nitride nano combustion catalyst comprises a Ni 3 N nano combustion catalyst, an O-doped Ni 3 N nano combustion catalyst and a molybdenum, vanadium or chromium-doped Ni 3 N nano combustion catalyst; the nickel-based nitride nano combustion catalyst is prepared by adopting a precursor of high-temperature nitriding NiO nano sheets, the NiO nano sheets are prepared by combining hydrothermal synthesis with a high-temperature annealing method, the adjustment of the oxygen-nitrogen ratio is realized by changing the nitriding temperature, and the bimetal structure is realized by introducing other transition metal precursors into a hydrothermal reaction solution. Specifically, the preparation method comprises the following steps:
Step 1, preparation of Ni (OH) 2 nanosheet precursors:
Preparing Ni (OH) 2 nano-sheets by adopting a hydrothermal method, wherein the raw materials of the hydrothermal method comprise nickel salt, urea and NH 4 F, the hydrothermal reaction temperature is 120 ℃, and the reaction time is 9 hours; cooling to room temperature, centrifuging, washing the centrifugal precipitate with deionized water and ethanol for three times, and drying in a vacuum oven at 60 ℃ for more than 12 hours to obtain green powdery product Ni (OH) 2 nano-sheets; the nickel salt in the step 1 is one of nickel nitrate, nickel acetate and nickel acetylacetonate, and the content is 0.5-2 mmol;
step2, preparing a NiO nano-sheet precursor:
Annealing the Ni (OH) 2 nano sheet obtained in the step 1 in an argon atmosphere for 2 hours to obtain a NiO precursor;
step 3, high temperature nitridation of the NiO nanosheet precursor:
And (3) nitriding the NiO precursor prepared in the step (2) in an ammonia atmosphere to obtain the nickel-based nitride nano combustion catalyst.
When preparing the Ni 3 N nano-combustion catalyst, the molar ratio of nickel salt, urea and NH 4 F in step 1 is 1: (2-5): (1-3); the annealing temperature in the step 2 is 300-650 ℃, and the argon flow rate is 100-300 mL/min; the nitriding temperature in the step 3 is 350-600 ℃, the nitriding time is 2h, the flow rate of ammonia gas is 80-180 mL/min, and the nickel-based nitride nano combustion catalyst prepared at the moment is Ni 3 N nano combustion catalyst.
When preparing the O-doped Ni 3 N nano-combustion catalyst, the molar ratio of nickel salt, urea and NH 4 F in step 1 is 1: (2-5): (1-3); the annealing temperature in the step 2 is 300-650 ℃, and the argon flow rate is 100-300 mL/min; the nitriding temperature in the step 3 is 350 ℃, the nitriding time is 1.5h, the ammonia flow rate is 80-180 mL/min, and the nickel-based nitride nano combustion catalyst prepared at the moment is an O-doped Ni 3 N nano combustion catalyst.
When preparing the molybdenum, vanadium or chromium doped Ni 3 N nano combustion catalyst, in the step1, the raw materials of the hydrothermal method further comprise a transition metal precursor, wherein the transition metal precursor is one of molybdate, vanadate and chromate, and the mole ratio of nickel salt, transition metal precursor, urea and NH 4 F is 1:0.1: (2-5): (1-3) obtaining Mo doped Ni (OH) 2 nano-sheet precursor through the step 1; the annealing temperature in the step 2 is 300-650 ℃, the argon flow rate is 100-300 mL/min, and the Mo-doped NiO nano-sheet precursor is obtained through the step 2; the nitriding temperature in the step 3 is 350-600 ℃, the nitriding time is 2h, the flow rate of ammonia gas is 80-180 mL/min, and the nickel-based nitride nano combustion catalyst prepared at the moment is a molybdenum, vanadium or chromium doped Ni 3 N nano combustion catalyst.
The following specific embodiments of the present application are provided, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of the present application fall within the protection scope of the present application.
Example 1: preparation of Ni 3 N nano combustion catalyst
Step 1, preparation of Ni (OH) 2 nanosheet precursors:
Ni (OH) 2 nano-sheets are prepared by a hydrothermal method, a hydrothermal reaction solution comprises 1mmolNi (NO 3)2·6H2 O, 4.4mmol of urea CO (NH 2)2 and 1.8mmol of NH 4 F solution), the hydrothermal temperature is 120 ℃ for 9 hours, the reaction solution is cooled to room temperature and then centrifuged to separate samples, the centrifugal precipitate is washed three times by deionized water and ethanol, and then dried in a vacuum oven at 60 ℃ for more than 12 hours to obtain green powdery Ni (OH) 2.
Step 2, preparation of NiO nanosheet precursor
The green powdery Ni (OH) 2 prepared in the step 1 was further annealed in an argon atmosphere (argon flow rate of 150 mL/min) at 400℃for 2 hours to prepare a precursor of NiO.
Step 3, high temperature nitridation of NiO nanosheet precursor
And (3) nitriding the NiO precursor prepared in the step (2) in an ammonia atmosphere (the ammonia flow rate is 120 mL/min.) at 400 ℃ for 2 hours to prepare the Ni 3 N nano-material.
Example 2: preparation of O-doped Ni 3 N nano combustion catalyst
Step 1, preparation of Ni (OH) 2 nanosheet precursor
Ni (OH) 2 nano-sheets are prepared by a hydrothermal method, a hydrothermal reaction solution comprises 1mmolNi (NO 3)2·6H2 O, 4.4mmol of urea CO (NH 2)2 and 1.8mmol of NH 4 F solution), the hydrothermal temperature is 120 ℃ for 9 hours, the reaction solution is cooled to room temperature and then centrifuged to separate samples, the centrifugal precipitate is washed three times by deionized water and ethanol, and then dried in a vacuum oven at 60 ℃ for more than 12 hours to obtain green powdery Ni (OH) 2.
Step 2, preparation of NiO nanosheet precursor
The green powdery Ni (OH) 2 prepared in the step 1 was further annealed in an argon atmosphere (argon flow rate of 150 mL/min) at 400℃for 2 hours to prepare a precursor of NiO.
Step 3, high temperature nitridation of NiO nanosheet precursor
And (3) nitriding the NiO precursor prepared in the step (2) in an ammonia atmosphere at 350 ℃ for 1.5 hours (the ammonia flow rate is 120 mL/min.) to prepare the O-doped Ni 3 N nano material.
Example 3: preparation of Mo-doped Ni 3 N nano combustion catalyst
Step1, preparing a Mo doped Ni (OH) 2 nano-sheet precursor:
the Ni (OH) 2 nano-sheets are prepared by adopting a hydrothermal method, a hydrothermal reaction solution comprises 1mmolNi (NO 3)2·6H2O、0.1mmolNa2MoO4·2H2 O, 5mmol of urea CO (NH 2)2 and 2.5mmol of NH 4 F solution), the hydrothermal temperature is 120 ℃ for 9 hours, cooling to room temperature, centrifugally separating a sample, washing centrifugal precipitate with deionized water and ethanol for three times, and drying in a vacuum oven at 60 ℃ for more than 12 hours to obtain green powdery Mo doped Ni (OH) 2.
Step 2, preparing a precursor of the Mo-doped NiO nano-sheet:
And (3) annealing the green powdery Ni (OH) 2 prepared in the step (1) for 2 hours in an argon atmosphere (the argon flow rate is 120 mL/min) at 450 ℃ to prepare a precursor of Mo-doped NiO.
Step 3, high-temperature nitridation of the Mo-doped NiO nano-sheet precursor:
And (3) nitriding the NiO precursor prepared in the step (2) in an ammonia atmosphere (ammonia flow rate is 100 mL/min.) at 400 ℃ for 2 hours to prepare the Mo-doped Ni 3 N nano material.
The results of the above examples were characterized as follows:
FIG. 1 shows an electron micrograph and XRD pattern of Ni 3 N, and as can be seen from FIG. 1, the morphology of Ni 3 N is a two-dimensional ultrathin nanosheet. Fig. 2 shows an electron microscope photograph and an XRD pattern of O doped Ni 3 N, and as can be seen from fig. 2, the doped O is uniformly distributed in the Ni 3 N nanosheets, the doping of O does not affect the lattice constant of Ni 3 N, and the stability of the sample structure is ensured. Fig. 3 is an electron microscope photograph and XRD pattern of Mo doped Ni 3 N, and as can be seen from fig. 3, mo is uniformly distributed in Ni 3 N nanosheets and forms heterojunction of MoO 2 and Ni 3 N on the surface, and Mo doping does not affect the morphology of Ni 3 N nanosheets. Fig. 4 is a DSC curve of nickel-based nitride and commercial nickel oxide mixed with HATO, and it can be seen from fig. 4 that, compared with NiO, the Ni 3 N samples prepared in examples 1-3 can greatly reduce the decomposition temperature of HATO, exhibit good catalytic activity, and can greatly increase the exotherm of HATO by Mo doping, because the heterojunction between MoO 2 and Ni 3 N increases the electron transfer efficiency, which is more thorough in HATO decomposition, and helps to increase the combustion efficiency of the propellant.
Claims (1)
1. The application of the nickel-based nitride nano combustion catalyst is characterized by being used for catalytic decomposition of HATO; HATO is 5,5 '-bitetrazole-1, 1' -dioxydihydroxyamine salt;
The nickel-based nitride nano combustion catalyst comprises a Ni 3 N nano combustion catalyst, an O-doped Ni 3 N nano combustion catalyst and a molybdenum, vanadium or chromium-doped Ni 3 N nano combustion catalyst;
the preparation method of the nickel-based nitride nano combustion catalyst comprises the following steps:
Step 1, mixing raw materials of nickel salt, urea and NH 4 F for hydrothermal reaction, wherein the hydrothermal reaction temperature is 120 ℃, and the reaction time is 9 hours; cooling to room temperature, centrifuging, washing the centrifugal precipitate with deionized water and ethanol for three times, and drying in a vacuum oven at 60deg.C for more than 12 hr to obtain green powdery product; the nickel salt in the step 1 is one of nickel nitrate, nickel acetate and nickel acetylacetonate; the molar ratio of the nickel salt to the urea to the NH 4 F is 1: (2-5): (1-3);
Step 2, annealing the product obtained in the step 1 in argon atmosphere for 2 hours to obtain a precursor; the annealing temperature in the step 2 is 300-650 ℃, and the argon flow rate is 100-300 mL/min;
Step 3, nitriding the precursor prepared in the step2 in an ammonia atmosphere to obtain a nickel-based nitride nano combustion catalyst;
When the nitriding temperature in the step 3 is 350-600 ℃, the nitriding time is 2 hours, the flow rate of ammonia gas is 80-180 mL/min, and the nickel-based nitride nano combustion catalyst prepared at the moment is a Ni 3 N nano combustion catalyst;
When the nitriding temperature in the step 3 is 350 ℃, the nitriding time is 1.5h, the flow rate of ammonia gas is 80-180 mL/min, and the nickel-based nitride nano combustion catalyst prepared at the moment is an O-doped Ni 3 N nano combustion catalyst;
In the step 1, the raw materials of the hydrothermal reaction further include a transition metal precursor, wherein the transition metal precursor is one of molybdate, vanadate and chromate, and the molar ratio of nickel salt to transition metal precursor to urea to NH 4 F is 1:0.1: (2-5): (1-3); the nitriding temperature in the step 3 is 350-600 ℃, the nitriding time is 2 hours, and the ammonia flow rate is 80-180 mL/min; the nickel-based nitride nano combustion catalyst prepared at the moment is a Ni 3 N nano combustion catalyst doped with molybdenum, vanadium or chromium.
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