METHOD FOR PREPARING COPPER AZIDE AND CUPROUS AZIDE ENCAPSULATED BY CONDUCTIVE METAL-ORGANIC FRAMEWORK

Abstract

Provided is a method for preparing copper azide and cuprous azide encapsulated by conductive metal-organic framework. The method uses a conductive copper-containing metal-organic framework material as a precursor, and completes the azidation of the precursor by means of a liquid-solid electrochemical azidation reaction. Copper azide and cuprous azide nanocrystals are highly uniformly embedded within a conductive framework, which may effectively avoid the agglomeration of copper azide and cuprous azide, and reduce static charge generated by friction, displacement, and the like. Meanwhile, the conductive framework may promote the effective transfer of charge, avoid the accumulation of static charge, and improve the electrostatic safety. In addition, the liquid-solid electrochemical azidation reaction has advantages such as being safe and efficient, having a short reaction time and having strong operability, and the preparation process is compatible with a MEMS process, which is beneficial for the application of copper azide and cuprous azide materials in micro devices.

Claims

1. A method of preparing copper azide and cuprous azide encapsulated by conductive metal-organic framework (MOF) comprising: Conductive copper-containing MOF serves as the anode while N3 containing solution constitutes the electrolyte; the azide reaction of copper is induced on the MOF anode upon being energized; consequently, copper azide and cuprous azide encapsulated by conductive MOF is acquired after drying.

2. The method of claim 1, wherein the solvent of N.sub.3.sup.−-containing solution is water or low-density alcohol solution.

3. The method of claim 2, wherein the low-density alcohol solution refers to methanol or ethanol solution.

4. The method of claim 1, wherein the N.sub.3.sup.−-containing solution is the solution of sodium azide or potassium azide.

5. The method of claim 1, wherein the concentration of N.sub.3.sup.−-containing solution ranges from 0.01 mol/L to 1 mol/L.

6. The method of claim 1, wherein the copper-containing conductive MOF refers to Cu(TCNQ) or Cu-CAT.

7. The method of claim 1, wherein the energized condition refers to modes of constant current or constant voltage.

8. The method of claim 7, wherein the current density ranges from 0.1 mA/cm.sup.2 to 10 mA/cm.sup.2 when constant current is applied.

9. The method of claim 1, wherein the azidation time ranges from 1 min to 240 min.

10. The method of claim 2, wherein the concentration of N.sub.3.sup.−-containing solution ranges from 0.01 mol/L to 1 mol/L.

11. The method of claim 3, wherein the concentration of N.sub.3.sup.−-containing solution ranges from 0.01 mol/L to 1 mol/L.

12. The method of claim 4, wherein the concentration of N.sub.3.sup.−-containing solution ranges from 0.01 mol/L to 1 mol/L.

13. The method of claim 2, wherein, the copper-containing conductive MOF refers to Cu(TCNQ) or Cu-CAT.

14. The method of claim 3, wherein the copper-containing conductive MOF refers to Cu(TCNQ) or Cu-CAT.

15. The method of claim 4, wherein the copper-containing conductive MOF refers to Cu(TCNQ) or Cu-CAT.

16. The method of claim 2, wherein the energized condition refers to modes of constant current or constant voltage.

17. The method of claim 3, wherein the energized condition refers to modes of constant current or constant voltage.

18. The method of claim 4, wherein the energized condition refers to modes of constant current or constant voltage.

Description

DESCRIPTIONS OF PICTURES

[0020] FIG. 1 shows XRD patterns of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5.

[0021] FIG. 2 shows SEM image of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5.

[0022] FIG. 3 shows HRTEM image of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5.

[0023] FIG. 4 shows TG-DCS curve of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5.

[0024] FIG. 5 shows electrostatic sensitivity image of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5.

DETAILED DESCRIPTION

[0025] Details of this invention are further depicted with reference to the examples and diagrams. The implementation of this invention is much more than depiction.

[0026] The preparation of Cu(TCNQ) refers to the literature (Liu H, Liu Z, Qian X, et al. Field emission and electrical switching properties of large-area CuTCNQ nanotube arrays. Crystal Growth & Design, 2009, 10(1): 237-243.). Cu(TCNQ) is prepared by immersion method on copper substrate.

[0027] The preparation of Cu-CAT refers to the literature (Hmadeh M, Lu Z, Liu Z, et al. New porous crystals of extended metal-catecholates. Chemistry of Materials, 2012, 24(18): 3511-3513.). Cu-CAT is obtained by solvothermal method.

EXAMPLE 1

[0028] Cu(TCNQ) film served as the anode and water solution of 0.01 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 0.1 mA/cm.sup.2 and 240 min, respectively. Cu(TCNQ) completed its azidation on the anode. Finally, copper azide and cuprous azide film encapsulated by Cu(TCNQ) was obtained after drying.

EXAMPLE 2

[0029] Cu(TCNQ) film served as the anode and water solution of 0.02 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 0.1 mA/cm.sup.2 and 240 min, respectively. Cu(TCNQ) completed its azidation on the anode. Finally, copper azide and cuprous azide film encapsulated by Cu(TCNQ) was obtained after drying.

EXAMPLE 3

[0030] Cu(TCNQ) film served as the anode and water solution of 1 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 0.1 mA/cm.sup.2 and 120 min, respectively. Cu(TCNQ) completed its azidation on the anode. Finally, copper azide and cuprous azide film encapsulated by Cu(TCNQ) was obtained after drying.

EXAMPLE 4

[0031] Cu(TCNQ) film served as the anode and water solution of 0.02 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 0.1 mA/cm.sup.2 and 1 min, respectively. Cu(TCNQ) completed its azidation on the anode. Finally, copper azide and cuprous azide film encapsulated by Cu(TCNQ) was obtained after drying.

EXAMPLE 5

[0032] Cu(TCNQ) film served as the anode and water solution of 0.02 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 0.1 mA/cm.sup.2 and 60 min, respectively. Cu(TCNQ) completed its azidation on the anode. Finally, copper azide and cuprous azide film encapsulated by Cu(TCNQ) was obtained after drying.

[0033] Among the foregoing examples, Cu(TCNQ)-encapsulating copper azide and cuprous azides feature similar structures, morphology and performance. Cu(TCNQ)-encapsulating copper azide and cuprous azide prepared in Example 5 was exhibited. The morphology and performance are characterized and depicted as follows.

[0034] FIG. 1 shows XRD patterns of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5, indicating that the resulting products mainly consist of cuprous azide, copper azide and Cu(TCNQ).

[0035] FIG. 2 shows SEM image of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5, indicating that the morphology of resulting products is flake array.

[0036] FIG. 3 shows HRTEM image of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5, indicating that the resulting copper azide nanocrystals are highly homogeneously embedded in the Cu(TCNQ) framework.

[0037] FIG. 4 shows TG-DSC curves of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5, indicating that two exothermic peaks represent the rapid decomposition reaction of cuprous azide and copper azide, respectively.

[0038] FIG. 5 shows electrostatic sensitivity image of Cu(TCNQ)-encapsulating copper azide and cuprous azide films with Cu(TCNQ) as the precursor in Example 5. After encapsulating copper azide and cuprous azide in highly conductive Cu(TCNQ) framework, the electrostatic sensitivity receives a distinct reduction and safety performance gains a great improvement

CONTRASTIVE EXAMPLE 1

[0039] CuO film served as the anode and water solution of 0.02 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 1 mA/cm.sup.2 and 10 min, respectively. CuO completed its azidation on the anode. Finally, copper azide film was obtained after drying.

TABLE-US-00001 TABLE 1 Comparison for the electrostatic sensitivity of copper azide and cuprous azide prepared by electrochemical azidation with different precursors Precursor CuO Cu(TCNQ) Electrostatic Sensitivity (mJ) 1.0 12.3

[0040] As shown in Table.1, the electrostatic safety of copper azide and cuprous azide with Cu(TCNQ) as precursor dramatically outperforms that of copper azide and cuprous azide with CuO as precursor.

EXAMPLE 6

[0041] Cu(TCNQ) film served as the anode and water solution of 0.02 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 1 mA/cm.sup.2 and 10 min, respectively. Cu(TCNQ) completed its azidation on the anode. Finally, copper azide and cuprous azide film encapsulated by Cu(TCNQ) was obtained after drying.

EXAMPLE 7

[0042] Cu(TCNQ) film served as the anode and water solution of 0.02 mol/L sodium azide constituted the electrolyte. The current density and azidation time were 10 mA/cm.sup.2 and 10 min, respectively. Cu(TCNQ) completed its azidation at anode. Finally, copper azide and cuprous azide film encapsulated by Cu(TCNQ) was obtained after drying.