CN113667139B - High-energy silver cluster-based assembled ignition material and preparation method thereof - Google Patents
High-energy silver cluster-based assembled ignition material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the crossing field of nanoclusters and coordination chemistry, and discloses a novel high-energy cluster assembled ignition material and a preparation method thereof. It uses metal cluster as structural node and contains energy bridging ligandThe 1-propargyl imidazole is connected to form the silver cluster base assembly material. The chemical formula is as follows: ag12(CF3COO)6(C6H5N2)6(ZZU‑361)、Ag14(CF3COO)6(C6H5N2)8(ZZU‑362)、Ag8(C6H5N2)4(NO3)4(ZZU-363), wherein the compounds ZZU-363 have a large amount of energy-containing nitrate radical and a unique molecular structure, so that excellent ignition performance is presented, the ignition delay time reaches 26ms, and the volume energy density reaches 40.4kJ cm‑3. The material can meet the requirement of modern spacecraft on propellant, and can be used as fuel of space engines.
Description
Technical Field
The invention belongs to the crossing field of nanocluster and coordination chemistry, and particularly relates to a novel ignition material capable of realizing high-energy cluster assembly and a preparation method thereof.
Background
The ignition material is used as a power source of rockets and spacecrafts, and the provided power determines the height, the voyage and the service life of the spacecrafts. However, some of the rocket propellants commonly used today, such as the Alterlas-semi-human horse rocket, are in liquid H2/O2As a propellant, the long third rocket is made of unsym-dimethyl hydrazine/N2O4As a propellant, it has some significant disadvantages: the environment-friendly and environment-friendly type air-conditioning agent has extremely strong toxicity and carcinogenicity, extremely harsh storage conditions and the like, and in addition, serious accidents also happen in the history of space flight, so that serious pollution and great economic loss are caused. With the increasing environmental pollution and the safety requirements of aircraft, the possible threat of toxicity and instability of the propellant needs to be avoided as much as possible.
In recent years, ionic liquid spontaneous ignition materials are widely researched, but currently, human beings do not deeply research ionic liquid, some potential hazards of the ionic liquid are not known, and most of common ionic liquids have high corrosivity and are easy to severely corrode metals. It has been reported that the metal cluster material has a large number of catalytic active centers and can improve the ignition performance as a hot spot, but the cluster materials have a problem of insufficient output energy due to weak van der waals force. Accordingly, there is a need to develop a new propellant material with superior properties to replace the deficiencies of existing autoignition materials in storage and use.
Disclosure of Invention
In order to develop a novel and high-energy spontaneous combustion ignition material, the invention aims to synthesize the spontaneous combustion ignition material with high energy and excellent ignition performance, and solve the problem that the ignition performance and the high energy of the traditional spontaneous combustion material are difficult to be considered; another object is to provide a process for the preparation thereof.
Considering that conventional clusters are only bonded by weak van der waals forces, energy is not well supplied. Therefore, the invention aims to form the cluster group assembled ignition material with higher energy and enthalpy of formation by coordination bond connection on the basis of the abundant active catalytic sites of clusters, so that the metal clusters are selected as the connecting nodes, and the high-energy organic ligand 1-propargyl imidazole is selected as the bridging part, thereby achieving the purpose of the invention.
The structural general formula of the silver cluster-based assembled ignition material is shown as the formula I:
wherein: ag clusters is a silver cluster structure formed by Ag-Ag interaction connection; the material is constructed into a three-dimensional structure through bridging of 1-propargyl imidazole ligands; the alkynyl and the imidazole N are respectively connected with silver atoms in the silver cluster; the silver cluster structure comprises Ag12、Ag14Or Ag1D。
The ignition assembly material is preferably Ag12(CF3COO)6(C6H5N2)6(ZZU-361)、Ag14(CF3COO)6(C6H5N2)8(ZZU-362)、Ag8(C6H5N2)4(NO3)4(ZZU-363). The crystal structures are all three-dimensional frames, and the coordination mode is shown in figure 1.
In order to obtain the silver cluster-based assembled ignition material, firstly, preparing a silver cluster precursor by using silver oxide and a 1-propargyl imidazole ligand in an ammonia solution; the silver cluster precursor, silver trifluoroacetate and copper nitrate metal salt are prepared by stirring at room temperature under the condition of using N, N-dimethylformamide, methanol or acetonitrile as a solvent.
The method is realized by the following steps:
1. firstly, the synthesis of propargyl imidazole silver: mixing silver oxide (Ag)2O) dissolving in ammonia water under the condition of ice-water bath, stirring until the solution is completely dissolved, slowly dripping 1-propargyl imidazole dissolved in ethanol into the silver oxide ammonia water solution, stirring for reaction, performing suction filtration after the reaction is finished, and washing and precipitating to obtain propargyl imidazole silver. Wherein the molar ratio of silver oxide/ammonia water/propargylimidazole is 1:2: 2.
2. ZZU-361: with Dimethylformamide (DMF)/methanol (CH)3OH) (v/v-2/1, 6mL) mixed with CF3The solution of COOH (10. mu.L) dissolved silver propargylimidazole (11.0mg,0.05mmol) and silver trifluoroacetate (11mg,0.05mmol), stirred overnight, filtered and the supernatant evaporated at room temperature to give crystals.
ZZU-362 Synthesis: with Dimethylformamide (DMF)/methanol (CH)3OH) mixed with CH3The solution of CN dissolved silver propargylimidazole (11.0mg,0.05mmol) and silver trifluoroacetate (11mg,0.05mmol), stirred overnight, filtered and the clear solution evaporated at room temperature to give crystals. DMF/CH3OH/CH3CN(v/v/v＝1/1/1,6mL)。
ZZU-363 Synthesis: with dimethylformamide/methanol in admixture with CF3Dissolving silver propargylimidazole and silver trifluoroacetate in the solution of COOH, and adding Cu (NO)3)2Filtering the ethanol solution, and volatilizing the clear solution at room temperature to obtain crystals.
The material takes a metal silver cluster as a node, a three-dimensional framework material is formed by bridging through 1-propargylimidazole (PIm) bidentate ligands, the middle metal cluster as a node is connected through alkynyl and N on the ligands, and finally, a three-dimensional framework structure is generated by infinite extension in space. ZZU-363, because of their unique structure, the metal atoms are connected by Ag-Ag metal interaction to form a one-dimensional chain structure, and the adjacent chains are connected by organic ligands. Thereby forming a three-dimensional spatial structure (shown in fig. 2-4).
The designed and synthesized metal cluster assembly material can realize faster ignition time with white fuming nitric acid oxidant, which is respectively 60ms, 59ms and 26 ms. Due to the faster ignition time, and the higher output energy, the aircraft can be used as a potential power source of the spacecraft to provide flight power (figure 5).
Meanwhile, the reaction process and the intermediate change of the reaction are studied in detail by theoretical calculation, wherein the analysis is carried out from the band gap firstly, the ignition capability is closely related to the band gap of the material, the narrower band gap usually means excellent ignition performance, and conversely, the wide band gap is not favorable for ignition. In addition, the electrostatic potential is often one of the important means for researching the ignition performance of the material, and during the reaction process, the lower electrostatic potential often means that the material is more easily attacked by an electrophilic reagent, so that the material is more easily combined with nitric acid molecules, and the ignition is favorably generated. Gibbs free energy reflects the energy barrier of material reaction more intuitively, and higher energy barrier indicates that more energy needs to be overcome for reaction and the reaction is difficult to occur. Thus, the structural characteristics of ZZU-363, as well as the peripheral ligands, were found to be more susceptible to the initiation reaction during the comparison of the three materials.
The invention has the advantages that: on the basis of the active catalytic sites rich in clusters, the cluster-based assembled ignition material with higher energy and enthalpy of formation is formed through coordination bond connection, and the volume energy densities of ZZU-361, ZZU-362 and ZZU-363 are respectively 31.4kJ cm-3、34.5kJ cm-3And 40.4kJ cm-3Energy density is an important criterion for the measurement of propellant ignition materials. The materials are respectively placed in environments with different humidity, and are kept still for three days, and PXRD tests show that the materials can well keep the stability of the structure. Wherein the compounds ZZU-363 contain a large amount of energy-containing nitrate radical and a unique molecular structure, thereby showing excellent ignition performance and achieving ignition delay timeTo 26ms, the volume energy density is up to 40.4kJ cm-3. The material can well meet the requirements of modern spacecrafts on propellants. The material can be used as fuel of an aerospace engine due to excellent ignition performance and higher output energy.
Drawings
FIG. 1 shows the three-dimensional structure and coordination mode of ZZU-361, ZZU-362, ZZU-363 crystals.
FIG. 2 shows specific coordination patterns of crystals ZZU-361, wherein a) the coordination pattern of propargyl imidazole ligands in the structure, b) the coordination of the metal cluster core and surrounding ligands, and c) the assembly into a three-dimensional framework structure.
FIG. 3 shows specific coordination patterns of ZZU-362 crystals, wherein a b c) coordination patterns of propargylimidazole ligands in the structure, d) coordination of metal cluster cores and surrounding ligands, and e) assembly into a three-dimensional framework structure.
FIG. 4 shows coordination patterns of ZZU-363 crystals, wherein a) coordination patterns of propargyl imidazole ligands in the structure, b) distribution of abundant nitrate groups in the structure, c) coordination of metal cluster cores and surrounding ligands, and d) assembly into a three-dimensional framework structure.
FIG. 5 shows the ignition performance of the material of the present invention.
Fig. 6 is a graph of gibbs free energy barrier for the study of catalytic intermediate processes and respective reactions by theoretical calculations.
Detailed Description
The invention is further illustrated by the following examples:
example 1: the invention is synthesized from ZZU-361, ZZU-362 and ZZU-363
(1) Synthesis of propargyl imidazole silver: mixing silver oxide (Ag)2O) dissolving in ammonia water under the condition of ice-water bath, stirring until the solution is completely dissolved, then slowly dripping 1-propargyl imidazole dissolved in ethanol into the silver oxide ammonia water solution, stirring for reaction, performing suction filtration after the reaction is finished, and washing and precipitating by using ethanol and ether to obtain the propargyl imidazole silver. Wherein the molar ratio of silver oxide/ammonia water/propargylimidazole is 1:2: 2.
(2) ZZU-361: with Dimethylformamide (DMF)/methanol(CH3OH) (v/v 2/1, 6mL) mixed with CF3The solution of COOH (10. mu.L) dissolved silver propargylimidazole (11.0mg,0.05mmol) and silver trifluoroacetate (11mg,0.05mmol), stirred overnight, filtered and the clear solution evaporated at room temperature to give colorless transparent crystals in the form of a cake over several days.
ZZU-362: a similar procedure was used for the synthesis of ZZU-361, except that the solution was changed to DMF/CH3OH/CH3CN (v/v/v-1/1/1, 6mL), stirred at room temperature for 30 minutes, filtered and evaporated to give small colorless transparent crystals as a mass.
ZZU-363: on the basis of the synthesis of ZZU-361, Cu (NO) dissolved in 1mL of ethanol solution was added3)2(0.1mmol,24mg) solution, filtering, volatilizing for several days to obtain tiny crystals.
ZZU-361, ZZU-362, ZZU-363 from example 1 were further characterized as follows:
(1) ZZU-361, ZZU-362, ZZU-363 crystal structure
The X-ray single crystal diffraction data of the coordination polymers of the present invention were measured on a Rigaku XtaLAB Pro transtarget single crystal analyzer using appropriately sized single crystal samples. The data were all obtained with Cu-Ka monochromatized graphite
The rays are the diffraction source, are collected at 200K by the omega scanning mode, and are corrected by Lp factor and semiempirical absorption. The structure analysis is to obtain the initial structure by the direct method through the program SHELXT-2015, and then to refine the initial structure by the full matrix least square method through the program SHELXT-2015.
TABLE 1 Main crystallographic data
R1＝∑||Fo|-|Fc|/∑|Fo|.
Example 2:
ZZU-361, ZZU-362, ZZU-363: the materials are respectively placed in environments with different humidity, and are kept still for three days, and PXRD tests show that the materials can well keep the stability of the structure.
ZZU-361, ZZU-362, ZZU-363: using standard ignition test experiments, a quantity of ignition material (about 15mg) was selected in a 5mL glass container, placed in a room temperature environment, and a drop (about 30. mu.L) of WFNA was pipetted from a fixed height into the reaction vessel. From the instant the oxidant contacts the material, denoted reaction zero, until the first flame appears in the reaction vessel, and the intermediate time, denoted ignition delay time, it can be seen from the experimental results that the ignition delay time for materials ZZU-361 is 60ms, the ignition delay time for materials ZZU-362 is 59ms, and ZZU-363 is 26 ms. From the ignition time, the ignition time limit of the current spacecraft on the ignition material can be met. Because too fast and too slow the ignition time of the material is detrimental to the operation of an aerospace engine. The material can be used as fuel of an aerospace engine due to excellent ignition performance and higher output energy.
Energy density is another important criterion for measuring propellant ignition materials. The ignition materials prepared in the synthesis all have very high energy density. ZZU-361, ZZU-362 and ZZU-363 have a volumetric energy density of 31.4kJ cm-3、34.5kJ cm-3And 40.4kJ cm-3。
Research on intermediate products in the catalytic oxidation process of materials: the research of the intermediate products in the catalytic process is crucial to the proposal of the catalytic process and the mechanism. In order to study the catalytic oxidation path of the ignition material, theoretical calculation was used to study the catalytic process, and the reaction process was further studied by using the Vienna Ab initio Software Package (VASP) program, and it was found that, in the initial stage of the reaction process: firstly, the nitric acid molecules will be firstly neutralizedMaterial combination, HO-NO in nitric acid molecule during reaction process2The structure is bonded with the material through hydrogen bond interaction, then HO-N in the nitric acid molecule is broken, so that HO-is combined with silver atoms, and the nitric acid molecule releases NO2And the reaction is completed. Meanwhile, a large amount of heat is released, countless reactions are accumulated, the temperature is further increased, and finally, the ignition reaction is triggered.
Study of free energy during ignition of materials: further theoretical calculations using VASP show that a reaction intermediate with a higher energy level is required to be passed during the reaction, and the intermediate is the cleavage of the HO-N bond of the nitric acid molecule, and calculations show that the activation energy barrier of the reaction intermediate of ZZU-361 is 2.03eV, the activation energy barrier of the reaction intermediate of ZZU-362 is 1.70eV, and the activation energy barrier of ZZU-363 is 0.86eV, indicating that ZZU-363 is easier to perform during the reaction. In addition, the structure of ZZU-363 contains a large amount of nitrate to facilitate the combination with nitric acid. Taken together, materials ZZU-363 are more conducive to the reaction. Theoretical calculation and experimental results jointly prove the conclusion, and the correctness of the results is mutually verified.
Claims (8)
1. A silver cluster-based assembled ignition material is characterized in that the structural general formula is shown as formula I:
wherein: ag clu is a silver cluster structure formed by Ag-Ag interaction and mutual connection; the material is constructed into a three-dimensional structure through bridging of 1-propargyl imidazole ligands; the alkynyl and the imidazole N are respectively connected with silver atoms in the silver cluster; the silver cluster structure comprises Ag12、Ag14Or Ag1D。
2. The silver cluster-based assembled ignition material of claim 1, wherein the assembled ignition material is Ag12(CF3COO)6(C6H5N2)6、Ag14(CF3COO)6(C6H5N2)8Or Ag8(C6H5N2)4(NO3)4。
3. The silver cluster-based assembled igniter material of claim 2, wherein the assembled igniter material is Ag12(CF3COO)6(C6H5N2)6Of a single crystal structureP-1The space group is formed by the space group,a =12.01740(10) Å，b =13.6445(2) Å，c =13.6994(2) Å，α=113.491(2) °，β=104.7130(10) °，γ=106.9600(10) °，V=1786.42(5) Å3。
4. the silver cluster-based assembled igniter material of claim 2, wherein the assembled igniter material is Ag14(CF3COO)6(C6H5N2)8Of a single crystal structure ofP21/cThe space group is formed by the space group,a =13.2636(6)Å，b =21.0964(8) Å，c =16.3979(9)Å，α= 90°，β=90.088(4)°，γ=90°，V=4588.4(4)Å3。
5. the silver cluster-based assembled igniter material of claim 2, wherein the assembled igniter material is Ag8(C6H5N2)4(NO3)4Of a single crystal structureP4/nccThe space group is formed by the space group,a =16.38990(10) Å，b = 16.38990(10)Å，c =14.3453(2)Å，α=90 °，β=90°，γ=90°，V=3853.56(7)Å3。
6. a method of making the silver cluster-based assembled ignition material of claim 2, comprising the steps of:
(1) synthesis of propargyl imidazole silver: dissolving silver oxide in ammonia water under the condition of ice-water bath, stirring until the silver oxide is completely dissolved, slowly dripping 1-propargyl imidazole dissolved in ethanol into the ammonia water solution of the silver oxide, stirring for reaction, performing suction filtration after the reaction is finished, and washing and precipitating to obtain propargyl imidazole silver;
（2）Ag12(CF3COO)6(C6H5N2)6the synthesis of (2): with dimethylformamide/methanol in admixture with CF3Dissolving propargyl imidazole silver and silver trifluoroacetate in the COOH solution, stirring overnight, filtering, and volatilizing clear liquid at room temperature to obtain crystals; ag14(CF3COO)6(C6H5N2)8The synthesis of (2): with dimethylformamide/methanol in admixture with CH3Dissolving propargyl imidazole silver and silver trifluoroacetate in CN solution, stirring overnight, filtering, and volatilizing clear solution at room temperature to obtain crystals;
Ag8(C6H5N2)4(NO3)4the synthesis of (2): with dimethylformamide/methanol in admixture with CF3Dissolving silver propargylimidazole and silver trifluoroacetate in the solution of COOH, stirring overnight, and adding Cu (NO)3)2Filtering the ethanol solution, and volatilizing the clear solution at room temperature to obtain crystals.
7. Use of a silver cluster based assemble ignition material according to any of claims 1-5, characterized in that it is contacted with fuming nitric acid to spontaneously ignite as an igniter.
8. Use of a silver cluster based assembled ignition material according to any of claims 1 to 5, characterized in that it is applied to a spacecraft propellant.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106854286A (en) * | 2016-12-22 | 2017-06-16 | 郑州大学 | A kind of sulfydryl silver cluster coordination polymer, its preparation method and its application |
| CN110330513A (en) * | 2019-07-31 | 2019-10-15 | 郑州大学 | A kind of high stable shines by force the chiral nano silver clustered materials of high quantum production rate |
| CN111943964A (en) * | 2020-08-26 | 2020-11-17 | 辽宁石油化工大学 | Twenty-eight-core silver alkyne cluster material constructed by taking molybdic polyacid as anion template and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854286A (en) * | 2016-12-22 | 2017-06-16 | 郑州大学 | A kind of sulfydryl silver cluster coordination polymer, its preparation method and its application |
| CN110330513A (en) * | 2019-07-31 | 2019-10-15 | 郑州大学 | A kind of high stable shines by force the chiral nano silver clustered materials of high quantum production rate |
| CN111943964A (en) * | 2020-08-26 | 2020-11-17 | 辽宁石油化工大学 | Twenty-eight-core silver alkyne cluster material constructed by taking molybdic polyacid as anion template and preparation method thereof |
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