CN109437125A - A kind of synthesis annular N5The method of-metal salt - Google Patents
A kind of synthesis annular N5The method of-metal salt Download PDFInfo
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- CN109437125A CN109437125A CN201811248988.8A CN201811248988A CN109437125A CN 109437125 A CN109437125 A CN 109437125A CN 201811248988 A CN201811248988 A CN 201811248988A CN 109437125 A CN109437125 A CN 109437125A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0625—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with copper
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a kind of synthesis annular N5ˉThe TiFe_xM_y alloy of the method for metal salt, the most stable of structure of compound a certain for specified pressure, each atom is calculated using following formula: Hf(CuNx)=[H (CuNx)‑H(CuN3)‑(x‑3)H(N2)/2]/(x+1) wherein HfIt is the enthalpy of formation of each atom, H is the calculating enthalpy of a chemical unit of each compound, CuNxAnd CuN3Enthalpy H be to be obtained by calculating the structure of minimum energy that CALYPSO method is searched under set pressure.The beneficial effects of the invention are as follows with Cu (N3)2Contain N for what can be stabilized under forerunner's synthesis normal temperature and pressure conditions5 ˉThe CuN of anion5。
Description
Technical field
The invention belongs to compound technicals, are related to a kind of synthesis annular N5 ˉThe method of metal salt.
Background technique
Due to potential application foreground of the high Energy Density Materials in terms of explosive or propellant, make annular pentazole N5 ˉChemical combination
The design and synthesis of object become the hot spot of research.Recently, the different type that can be stabilized in atmospheric conditions has been synthesized
Annular N5 ˉCompound: (N5)6(H3O)3(NH4)4Cl、[Na(H2O)(N5)2]·2H2O,[M(H2O)4(N5)2]·4H2O, (M=
Mn,Fe,Co,and Zn)、[Mg(H2O)6(N5)2]·4H2), and 3D metallic organic frame complex [Na O8(N5)8(H2O)3]n。
However, these N5 ˉContaining the ion or group for being free of energy to enhance the stability of compound in compound, to reduce energy
Metric density.In order to increase the energy density of material, need to design the pentazole salt complex for containing minimum non-energy component.Preferably only
Use metal cation or H+To stablize annular N5 ˉAnion.Nearest Hu Ping Cheng professor and his colleagues report a kind of without molten
The pentazole salt complex AgN of agent5With a kind of 3D frame [Ag (NH3)2]+[Ag3(N5)4]ˉ, by silver and annular N5 ˉAnion is constituted.
Unfortunately, due to which photic decompose and/or be thermally decomposed into AgN3, these annulars N5 ˉCompound cannot be separated into pure AgN5.Success
Synthesize pure N5 ˉAnion salt still has huge challenge.
The synthesis of the more nitrogen solids for being introduced as high nitrogen-containing of pressure provides another way, and high pressure helps to destroy nitrogen
Tri- key of NN of gas intramolecular and then the non-molecule crystalline phase for forming fine and close nitrogen.Gathered by cube more nitrogen of deflection that singly-bound nitrogen-atoms forms
Closing object (cg-N) is exactly the Buddha's warrior attendant heated at the temperature greater than 2000K and the pressure higher than 110GPa using laser by dinitrogen
The synthesis of stone opposed anvils.Due to the strong electrostatic repulsion between the lone pair electrons of nitrogen-atoms, cg-N is restored to molecule N in 42GPa2
Solid.Nearest theory and experimental work all shows that alkali metal element is added into purity nitrogen system is conducive to metal ring N5 ˉSalt
High-pressure synthesis.Addition alkali metal element can not only transfer an electron to N5Ring, but also N can be realized by ionic bond5 ˉ
Armaticity and stabilization.2017, E.Stavrou, II Oleynik and its colleague report that they pass through in diamond anvil cell
Cesium azide (CsN is heated with laser3) and N2Cryogenic liquid successfully synthesizes metal ring N5 ˉSalt, synthesis pressure is 60
GPa can be stored in the environment of 18GPa or more.This year, P.Loubeyre et al. report pass through compression and laser
Heating is embedded in N2Lithium in molecule, available pentazole acid lithium solid, experiment synthesis pressure is 45GPa.However, all previous
Studies have shown that under high pressure, in X-N (X is alkali metal element) compound of different ratio, XN5And do not have minimum energy
Amount.Under normal temperature and pressure conditions, stable compound is alkali metal nitride (X3) and alkali metal azide (XN N3)。
When 100GPa, the proportion of minimum energy is 1:1 in Na-N and Rb-N compound.When pressure is 10GPa, Li-N system, energy
That minimum is Li2N2, further study showed that Li3N has minimum energy at 100GPa.Due to XN5Without minimum energy
Amount, it is meant that in synthesis XN5When need strict control synthesis condition (reaction time, temperature and pressure) and alkali metal and nitrogen
Ratio.This makes it difficult to synthesize on a large scale and using N5 ˉMetal salt.Copper azide, including CuN3With Cu (N3)2, belong to transition gold
Belong to azide.At normal temperatures and pressures, copper azide is typical ionic crystals, by copper cation and linear rodlike anion N3 ˉ
Composition, copper atom lose one or two electronics as electron donor respectively.Under high pressure, copper atom is expected to what offer did not occupied
For 4s and 4p track to accommodate the lone pair electrons of N atom and form coordinate bond with N atom, this is steady by greatly Reinforced Cu-N system
It is qualitative.
So far not yet synthesis can existing N at normal temperatures and pressures5- anionic metal salt, this greatly hampers its conduct
The application of high Energy Density Materials.Here it is proposed that a simple route of synthesis: by compressing CuN6Salt synthesizes annular N5 ˉMetal salt.Utilize first-principles calculations and search structure, it has been found that there is annular N5 ˉThe CuN of anion5Compound is 50
There is minimum energy in the pressure limit of~100GPa.At normal temperatures and pressures, CuN5By the annular N alternately connected5 ˉAnion
And Cu2+Cation forms zigzag chain structure.Copper N5 ˉSalt is that have good thermal stability and dynamic stability.Normal
It is the semiconductor with the band gap of 2.5eV under the conditions of normal temperature and pressure.To the further of characteristic electron, analysis shows, Cu atom is not only
Electronics is contributed to change N5Ring at bonded state, but also accommodate using empty outer shell track the lone pair electrons of N atom, shape
Increase the stability of system at coordinate bond.
Summary of the invention
The purpose of the present invention is to provide a kind of synthesis annular N5ˉThe method of metal salt, the beneficial effects of the invention are as follows conjunctions
At copper N5 ˉSalt is with good stability.
The technical scheme adopted by the invention is that the most stable of structure of compound a certain for specified pressure, each atom
TiFe_xM_y alloy is calculated using following formula:
Hf(CuNx)=[H (CuNx)-H(CuN3)-(x-3)H(N2)/2]/(x+1),
Wherein HfIt is the enthalpy of formation of each atom, H is the calculating enthalpy of a chemical unit of each compound, CuNxWith
CuN3Enthalpy H be to be obtained by calculating the structure of minimum energy that CALYPSO method is searched under set pressure.
In the pressure limit of 50GPa to 100GPa, CuN5It is the compound of minimum energy under the conditions of rich nitrogen, exactly because
Its energy is relatively low, all to pass through the compression Cu (N in certain pressure limit3)2Synthesize CuN5。
Detailed description of the invention
Fig. 1 is to form CuN at 20GPa, 50GPa and 100GPa respectivelyxFormation break.Solid line indicates convex closure figure.In order to
It conveniently checks, the consecutive points being connected to using dotted line above convex closure；
Fig. 2 is CuN5The crystal structure of compound；
Fig. 3 is P21/m-CuN5Stability；
Fig. 4 is P21/m-CuN5Characteristic electron in 0GPa；
Specific embodiment
The present invention is described in detail With reference to embodiment.
The TiFe_xM_y alloy of the most stable of structure of compound a certain for specified pressure, each atom is calculated using following formula:
Hf(CuNx)=[H (CuNx)-H(CuN3)-(x-3)H(N2)/2]/(x+1)
Wherein HfIt is the enthalpy of formation of each atom, H is the calculating enthalpy of a chemical unit of each compound, CuNxWith
CuN3Enthalpy H be to be obtained by calculating the structure of minimum energy that CALYPSO method is searched under set pressure.For N2,
Known structure with Pa-3 symmetry be considered as in 0 to 100GPa pressure limit in dinitrogen phase have it is lower
TiFe_xM_y alloy.
Present invention research CuNxThe energy stability of system under high pressure, calculates various CuNxCompound arrives 100GPa 0
Pressure limit in TiFe_xM_y alloy, as shown in Figure 1.Under a certain pressure, the CuN on convex closure figurexCompound is defined as " steady
State " system is easiest to be tested synthesis；And whether the definition on convex closure figure is " metastable state ", can be taken by experiment synthesis
Certainly in the height that it decomposes potential barrier.With pressure increase, Cu-N system is mobile to rich nitrogen side.In 20GPa, CuN4And CuN6
With negative TiFe_xM_y alloy, CuN4TiFe_xM_y alloy it is minimum, this shows CuN4It is most stable of.Under the pressure of 50GPa, all calculating
The TiFe_xM_y alloy of stoichiometry be all negative.In different compounds, CuN5Minimum energy；CuN4And CuN6It is also stable state
System.At 100GPa, most stable of compound is still CuN5, and CuN4,CuN6And CuN7It is stable for being.Calculate knot
Fruit shows in the pressure limit of 50GPa to 100GPa, CuN5It is the compound of minimum energy under the conditions of rich nitrogen, because of its energy
It measures relatively low, it is possible to by compressing Cu (N in corresponding pressure limit3)2To synthesize CuN5。
In atmospheric conditions, compound CuN5(a and b in Fig. 2) possesses P21/ m symmetry.As shown in table 1, different
There are three types of non-equivalence N and a kind of Cu atoms for the position Wyckoff.Positioned at N5N in ring1Atom is connect with Cu atom, and connect
N5Ring and Cu atom form zigzag chain.Average itrogen-to-nitrogen bonds is a length of This and its in annular N5 ˉIn value it is very consistent.For
Simplified expression, hereafter this representation is P2 by we1/m-CuN5。
Fig. 2 is CuN5The crystal structure of compound.With P21The CuN of/m structure5(a) and (b), be located at difference
The nitrogen-atoms of the position Wyckoff is respectively designated as N1, N2 and N3.(c) under normal pressure, calculating has P21The CuN of/m structure5Electricity
Sub- localization function, equivalent face amount are 0.8.Lattice parameter (d) β and (e) a, b and c and be (f) unit cell volume with pressure change
Curve.
Table 1. has P2 at 0GPa1The CuN of/m structure5Cell parameter and atom site
Fig. 3 is P21/m-CuN5Stability.Under normal pressure, the DOS of (a) phonon spectra (b) phonon of calculating；(c) 300K's
At a temperature of, the image of balanced structure at the end of 15ps molecular dynamics simulation；(d) P2 when 300K1/m-CuN5Molecular dynamics mould
Quasi- gross energy fluctuation.
The stability of structure cannot be determined only by comparing enthalpy, because structure may be by Dynamic Kinetic stability
It influences.It can use and calculate phonon spectra and state density using super cell's method to check P21/m-CuN5Dynamic stability, such as scheme
Shown in 3a and 3b.In 0GPa, entire Brillouin region Phonon frequency is positive value, shows P21/m-CuN5Have at 0GPa
Good dynamic stability.
Then, we using 2 × 2 × 2 surpass born of the same parents and carry out first principle molecular dynamics simulation (FPMD), further to comment
Estimate P21/m-CuN5Thermodynamic stability.Analog temperature is the temperature of 300K, time step 1fs.As shown in Figure 3c, exist
The image of geometry clearly illustrates at the end of 15ps is simulated: the gross energy of system fluctuates near -1525.3eV, and annular
N5 ˉKeep its structural intergrity.This is the result shows that P21/m-CuN5Compound and annular N5 ˉHave under room temperature street good
Thermodynamic stability.
Fig. 4 is P21/m-CuN5Characteristic electron under normal pressure.(a) band structure；(b) and (c) be respectively Cu and N office
The domain density of states (DOS)；(d)P21/m-CuN5Band gap with pressure history.The electronic band structure of calculating shows: P21/m-
CuN5Compound is the semiconductor that band gap is 2.5eV, is similar to LiN5.With the increase of pressure, P21/m-CuN5Band gap it is significant
Reduce, 0eV is reached in 70GPa and forms the transformation of semiconductor to conductor.Since density Functional Calculation is typically resulted in energy gap
Seriously underestimate, therefore practical band gap will be greater than calculated result.With the increase of pressure, bond distance will reduce, so expand valence band and
Conduction band, therefore lead to the reduction of band gap.Surprisingly the 4p rail portion of copper is occupied, as shown in Fig. 4 b and c, and
Near Fermi surface, there are apparent orbital hybridizations for the 2p interorbital of the 4p track of Cu and N.Based on Bader analytical calculation P21/m-
CuN5In Cu atomic structure parameter (- 0.8e) indicate Cu atom lose 4s electronics and have+1 chemical valence, to generate the ring of copper
Shape N5 ˉMetal salt.The annular N of copper5 ˉMetal salt shows significant dynamic stability under, has good heat at room temperature
Stability, this differs markedly from alkali metal nitride and AgN5In annular N5 ˉAnion.
The present invention uses the method calculated based on CALYPSO search structure method and Density functional gross energy, has studied height
Depress CuNxThe structure and stability of system.Having determined a kind of new has annular N5 ˉThe CuN of anion5.Result of study shows
In the pressure limit of 50GPa to 100GPa, CuN5There is minimum energy in the Cu-N compound studied.The sound of calculating
Sub- dispersion and molecular dynamics show with annular N5 ˉCuN5It is with good stability at normal temperatures and pressures.To characteristic electron
It is further analysis shows, Cu atom not only contributes electronics to change N5The bond styles of ring, but also with empty housing track
The lone pair electrons of N are accommodated, to reach stable state.Most of all, these under modest pressure the result shows that compress
CuN6The annular N with good stability can be synthesized5 ˉMetal salt.
The above is only not to make limit in any form to the present invention to better embodiment of the invention
System, any simple modification that embodiment of above is made according to the technical essence of the invention, equivalent variations and modification,
Belong in the range of technical solution of the present invention.
Claims (2)
1. a kind of synthesis annular N5ˉThe method of metal salt, it is characterised in that: the most stable of knot of compound a certain for specified pressure
The TiFe_xM_y alloy of structure, each atom is calculated using following formula:
Hf(CuNx)=[H (CuNx)-H(CuN3)-(x-3)H(N2)/2]/(x+1)
Wherein HfIt is the enthalpy of formation of each atom, H is the calculating enthalpy of a chemical unit of each compound, CuNxAnd CuN3's
Enthalpy H is obtained by calculating the structure for the minimum energy that CALYPSO method is searched under set pressure.
2. according to a kind of synthesis annular N5 described in claim 1ˉThe method of metal salt, it is characterised in that: in 50GPa to 100GPa
Pressure limit in, CuN5It is the compound of minimum energy under the conditions of rich nitrogen, it can be by one because its energy is relatively low
Cu (N is compressed in fixed pressure limit3)2Synthesis contains N5 ˉThe CuN of anion5。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112661124A (en) * | 2021-01-12 | 2021-04-16 | 吉林大学 | Non-molecular polymeric phase material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757453A (en) * | 2012-07-16 | 2012-10-31 | 南开大学 | Multifunctional rare earth metal-organic framework and preparation method thereof |
| CN105860961A (en) * | 2016-05-05 | 2016-08-17 | 中国计量大学 | Infrared luminescent material for rare-earth metal-organic framework |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757453A (en) * | 2012-07-16 | 2012-10-31 | 南开大学 | Multifunctional rare earth metal-organic framework and preparation method thereof |
| CN105860961A (en) * | 2016-05-05 | 2016-08-17 | 中国计量大学 | Infrared luminescent material for rare-earth metal-organic framework |
Non-Patent Citations (1)
| Title |
|---|
| JIANFU LI等: "Simple Route to Metal cyclo-N5- Salt: High-Pressure Synthesis of CuN5", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661124A (en) * | 2021-01-12 | 2021-04-16 | 吉林大学 | Non-molecular polymeric phase material and preparation method thereof |
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Application publication date: 20190308 |