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Enhancing energetic performance of multinuclear Ag(I)-cluster MOF-based high-energy-density materials by thermal dehydration Xiaohui Ma, Chao Cai, Wujuan Sun, Wei-Ming Song, Yulong Ma, Xiangyu Liu, Gang Xie, Sanping Chen, and Sheng-Li Gao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b00834 • Publication Date (Web): 14 Feb 2019 Downloaded from http://pubs.acs.org on February 16, 2019

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ACS Applied Materials & Interfaces

Enhancing energetic performance of multinuclear Ag(I)-cluster MOFbased high-energy-density materials by thermal dehydration Xiaohui Ma,† Chao Cai,† Wujuan Sun,§ Weiming Song,† Yulong Ma,† Xiangyu Liu,*,† Gang Xie,‡ Sanping Chen,*,‡ Shengli Gao‡ †State

Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China ‡Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China §College of Chemistry & Chemical Engineering, Xi'an ShiYou University, Xi'an, 710065, China ABSTRACT: It is an enormous challenge to construct high-energy-density materials (HEDMs) meeting simultaneously requirements of high energy and excellent stability. In this work, the reaction of Ag(I) ion with the nitrogen-rich ligand, 1H-tetrazole-5-acetic acid (H2tza), leads to a novel Ag7-cluster metal-organic framework (MOF), [Ag7(tza)3(Htza)2(H2tza)(H2O)] (1), with remarkable highenergy content, stability and insensitivity. Dramatically, the heating-dehydrated process of 1 produces a new stable energetic material, [Ag7(tza)3(Htza)2(H2tza)] (1a), which features superior energy and undiminished safety performance compared with 1. KEYWORDS: metal-organic framework, high-energy materials, Ag-cluster, thermal dehydration, energetic property

Energetic materials play a pivotal role in both military and civilian applications, so a great amount of efforts have been made to obtain prominent HEDMs.1-3 With the growing variety in the applications of HEDMs, implementing an optimal integration of high-energy performance, outstanding thermostability and low sensitivity is currently an important goal for high-performant HEDMs.4-8 Recently, researches on high-energy MOFs (HE-MOFs) have constructed an ingenious approach for the stable energetic materials, that is, the MOFs with high-nitrogen content, assembled from metallic nodes with nitrogen-rich organics including azido, furazan and heterocyclic compounds via covalent interactions, are regarded as a potential candidate for a new generation of explosive.9 Compared with conventional organic explosives, such HEMOFs, especially three-dimensional (3D) MOFs with advanced structural reinforcement, have presented potential advantage such as higher density, remarkable insensitivity, and superior thermostability, which are the essential traits of HEDMs and could be achieved through wise screening of central ion and ligand. Therefore, the design and assembly of 3D HE-MOFs have become significant and challenging tasks. More importantly, the existing researches recognized that most of the three-dimensional high-nitrogen MOFs incorporate guest solvents coordinated with metallic ions or latticed in the pores.10,11 The attendance of these guest molecules not only generates the vapor tension at low-temperature area during the collapse process of the framework, which may cause the inferior safety, but also induces the reduction of the energy-

density and thus the decrease of heat of detonation.12,13 In this sense, more attempts should be performed to a develop rational strategy for the preparation of HE-MOFs, especially solventfree HE-MOFs, thereby obtaining high-performant HEDMs. For the time being at least, heterocyclic nitrogen and its derivatives are identified as a kind of splendid high-energy component for the construction of outstanding 3D HE-MOF, based on the diverse coordination patterns, intrinsically energetic N–N, N=N, C–N and C=N elements and stable structure.14 Meanwhile, the introduction of oxygen component in the nitrogen-rich heterocycle ligands has been widely considered as an effective strategy to rationalize the oxygen balance which is also a crucial criterion for the detonation property of the HE-MOFs.15 In view of this, a tetrazolecarboxylate ligand, 1H-tetrazole-5-acetic acid (H2tza), motivates our interests for the following key reasons: 1) Serving as a type of multidentate ligands, carboxylate-introduced tetrazole with four nitrogen atoms and two oxygen atoms potential binding metal ions would give rise to new HE-MOF with high mechanical strength, insensitivity, higher density, moderate oxygen balance and excellent energetic property; 2) Notably, the structural skeleton of tza-2 ring along with the centered sp3 carbon site between tetrazole and carboxyl ensure it possessing a possibility of reasonable distortion to sterically coordinate to metal center.16 Moreover, considering the high heat of detonation, Ag+ cation exhibiting various and flexible coordination manners is a promising option to assemble HEMOF with high density and intriguing architecture.17-20

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Figure 1. (a) Asymmetric unit of 1. (b) Coordination environments of Ag1-Ag7 in 1. (c) The coordination modes of organic ligands, (d) 3D structural framework of 1. (e) 3D topological network of 1. (Hydrogen atoms are omitted for clarity).

Based on the considerations above, a 3D HE-MOF, [Ag7(tza)3(Htza)2(H2tza)(H2O)] (1), has been successfully isolated and characterized. The heat of detonation and insensitivity of 1 precede those of traditional energetic materials. Noteworthily, a new water-free compound, [Ag7(tza)3(Htza)2(H2tza)] (1a), has been readily derived from the thermostatic dehydration of 1 (Scheme 1). As anticipated, compound 1a manifests more remarkable energetic performance and comparable structural stability compared with 1. The present contribution not only demonstrates the efficient and reasonable design to gain 3D HE-MOFs with dramatic energy, but also offers an alternative approach to improve the performance of high-energy materials.

Scheme 1 Synthetic route of 1 and 1a

Compound 1 was obtained as colorless and transparent crystal from hydrothermal synthesis of distilled water solution containing Ag(NO3)3 and H2tza (Scheme 1). The crystal structure of 1 was resolved by X-ray crystallography. Additional data for refinement details are given in the Supporting Information (Table S1-S3). Architecturally, 1 belongs to triclinic system (space group: P-1) and displays a 3D framework with the density (ρ) of 2.572 g cm-3. Seven crystallographically independent Ag ions (Ag1–Ag7), three tza2- anions, two Htza-1 anions, one H2tza ligand, and one coordinated water molecule coexist in the asymmetric unit (Figure 1a). An interesting scenario relying on the multiple

coordination configurations around the Ag ions has been observed in 1. For 1, the seven crystallographically unique Ag atoms are indicative of three types of coordination environments (Figure 1b): (i) Two metal ions (Ag1 and Ag2) are four-coordinated in a trigonal-pyramidal configuration. Each Ag ion in a {AgN4} chromophore is completed by four N atoms from different ligands. (N3, N8, N13 and N21 for Ag1; N2, N5, N9 and N22 for Ag2) (ii) Two centers (Ag3 and Ag4) adopt the trigonal planar geometry which is completed by three N atoms (N1, N6 and N10 for Ag3; N4, N7 and N14 for Ag4) from different H2tza molecules. (iii) Three cores (Ag5, Ag6 and Ag7) show the distorted trigonal-pyramid geometry containing Ag–O bonds. Ag6 lies in the coordination geometry of {AgN3O}, which consists of an oxygen atom of the coordinated H2O molecule (O1W) and three nitrogen atoms (N12, N15 and N19) of three H2tza groups. The Ag5 and Ag7 ions are also in {AgN3O} motif, but respectively associated with O atoms (O1 for Ag5; O3 for Ag7) from carboxylate groups of ligands, and three N atoms (N11, N16 and N20 for Ag5; N17, N23A and N24 for Ag7) from tetrazole rings of H2tza ligands. The ligands in the structure perform three different coordination modes, in which the tetrazole ring of H2tza spacers adopts µ4-1, 2, 3, 4 and µ4-1, 2, 4 modes to link with Ag(I) centers, respectively (Figure 1c). The Ag–N distances fall into the range 2.186(7)–2.399(7) Å, while the N–Ag–N angles are 93.4(3)°–146.2(3)°. The Ag(I) ions, which exhibit various coordination environments, are connected by the H2tza ligands with diverse coordination patterns, contributing to the construction of a compact 3D MOF (Figure 1d). A unique hydrogen-bonding observed in the structure is related to the coordinated water molecule (O1W– H⋯O1 = 2.77 Å) (Table S3). Obviously, saturated coordination sites of tetrazole components and H-bonding certainly lead to


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the prominent thermostability and insensitivity of the target MOF. The topology investigation indicates that the 3D network can be rationalized to a 3,3,3,3,4,4,4,4,4,4,4,5,5-connected net with the Point (Schlafli) symbol being {4.6.84}{4.6.8}2{42.6.83}2 {42.63.8}2{42.6} by denoting the Ag+ ions as 4,4,3,3,4,3,4-connected nodes and the ligands as 3,4,4,4,5,5-connected nodes, respectively (Figure 1e).

Figure 2. TG curves of 1 and 1a

Figure 3. Photographs of compound 1 (a) and 1a (b), and SEM images of 1 (c) and 1a (d)

The thermostability of 1 was recorded by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). As shown in Figure 2, first, a mass loss of 1.7% from 176 to 182 °C corresponds to the release of coordinated H2O molecule (calcd 1.2%); then a stable platform is observed in the range 190–250 °C, during which the coordinated H2O molecule is lost and the 3D framework of 1 maintains intact. With continuous heating, a stepwise mass loss in the temperature range 260–350 °C reflects the decomposition of the main structural framework. There are three main peaks in the DSC curve of 1. (Figure S1). The endothermic peak matches with the dehydration behavior (Tp = 180 °C), while the two exothermal peaks represent the segmental decomposition (Tp = 292 °C and 325 °C). Inspired by the observation above, 1 was heated at 200 °C for a day, yielding the brown homogenous powder of the dehydration product 1a (Scheme 1). IR spectra reveals that, compared to 1, no coordinated H2O molecule exists in 1a due to the absence of the peak at 3442 cm-1. The experimental PXRD plots of 1 and 1a are consistent with the theoretical curve of 1, indicating an intact framework upon dehydration (Figure S2). Despite all this, the surface morphology images show that the surface of the bulk materials

changes from smooth to rough when compound 1 thermally transforms to 1a (Figure 3), which blocks the possibility for probing into the crystal structure of 1a. The intactness of the main frameworks and large change of the material surface in two compounds have also been confirmed by SEM characterizations (Figure 3). TGA measurement of 1a indicates that a rapid mass loss appears from 250 to 310°C, mirroring the only one sharp peak with the temperature of 255 °C in the DSC curve (Figure S1). Although the decomposition temperature of 1a is slightly lower than that of 1, the thermostabilities of both compounds are close to HMX (280 oC) which is one of the most energetic materials commonly employed,21 and higher than that of reported 1D energetic MOFs (CHP, 194 oC) and 2D energetic MOFs (CHHP, 231 oC). Such situation is presumably attributed to the strongly structural reinforcement of 3D frameworks. A comparison of the TG and DSC curves shows that, obviously, 1a performs a relatively drastic decomposition process, which implies that even slight H2O molecule has a significant influence on the release of energy. The investigations demonstrate that the densities of both cases (2.589 g/cm3 for 1 and 2.566 g/cm3 for 1a) are much larger than that of the H2tza ligand (1.71 g/cm3), confirming that the combination of silver ions and organic ligands is conducive to achieving the energetic materials with high density. The drastic decomposition processes imply the potential detonation behaviors of 1 and 1a. Accordingly, it is necessary to evaluate the heats of detonation (Q) of two compounds and compare the values with those of classic explosives and other HE-MOFs. In principle, the Q value is significantly related to θ the standard molar enthalpy of formation (  f H m ) which can be deduced from the constant-volume combustion energy (ΔcU). The ΔcU values of 1 and 1a are determined to be –12293 ± 2.17 and -13021 ± 2.16 J·g-1, respectively. Subsequently, the θ standard molar enthalpies of combustion (  c H m ) can be extracted as -18835.78 ± 3.33 kJ·mol-1 (1) and -19718.81 ± 3.29 θ kJ·mol-1 (1a) based on the formulas  c H m = ΔcU + ΔnRT and Δn = ng(products) – ng(reactants) where ng is the total molar amount of gases, R = 8.314 J·mol-1·K-1 and T = 298.15 K. Thus, θ the calculated standard molar enthalpies of formation (  f H m ) for 1 and 1a at 298 K are 8930.22 ± 0.61 and 9706.25 ± 0.57 kJ·mol-1, respectively (see the Supporting Information). θ Obviously, 1a possesses a higher  f H m than 1, probably owing to the release of the coordinated H2O component. As the primary criterions for energetic materials, Q, detonation velocity (D) and detonation pressure (P) can be obtained by using two different methods in this work. Firstly, the commercial software EXPLO5 v6.016 was applied to estimate these detonation parameters of 1 and 1a according to θ the calculated  f H m values. The extracted Q, D and P parameters are 1.65 kcal·g-1 (4.28 kcal·cm-3), 6.88 km·s-1, and 37.0 GPa of 1, 1.78 kcal·g-1 (4.57 kcal·cm-3), 6.74 km·s-1, and 41.5 GPa of 1a, respectively (Table S4). Secondly, a new empirical method was employed to determine the detonation property of metal-bearing explosive.22 On account of the largest exothermal theory proposed by Kamlet-Jacobs equations,23 the estimated detonation reactions for two compounds are described by eqn (1) and (2), Ag7C18H19N24O13(s)→7Ag(s) + (65/4)C(s) + (19/2)H2O(g) + (7/4)CO2(g) + 12N2(g) (1) Ag7C18H17N24O12(s)→7Ag(s) + (65/4)C(s) + (17/2)H2O(g) + (7/4)CO2(g) + 12N2(g) (2)



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Table 1. Physicochemical parameters of 1, 1a and some energetic materials ρa

OB b

Tdec c

Qd

De

Pf

IS g

(g/cm3)

(CO2)(%)

(oC)

(kcal/g)

(km/s)

(Gpa)

(J)

(N)

1.92

8.016

34.54

>40

>360

1

2.572(2.589) i

-33.36

260

FS h

1a

2.566 i

-33.76

250

2.02

8.089

35.01

>40

353

TNT24

1.654

-74.0

244

0.897

7.178

20.50

15

353

RDX24

1.806

-21.6

210

1.386

8.600

33.92

7.5

120

HMX24

1.950

-21.6

280

1.320

8.900

38.39

7.4

-

CHP25

1.948

-11.48

194

1.250

8.225

31.73

0.5

-

NHP25

1.983

-11.48

220

1.370

9.184

39.69

-

-

CHHP25

2.000

-13.05

231

0.750

6.205

17.96

0.8

-

{Ag2(DNMAF)(H2O)226

2.545

-7.69

230

1.95

9.673

50.01

10

160

{Ag2(DNMAF)}26

2.796

-8.16

212

2.19

10.242

58.30

8

120

[Ag(atrz)1.5(NO3)]n27

2.16

-50

257

1.381

7.773

29.70

30

-

Density from crystal structure. b Oxygen balance. c Thermal decomposition temperature. d Heat of detonation. e Detonation velocity. f Detonation pressure. g Impact sensitivity. h Friction sensitivity. i Density from Automatic Density Analyzer. TNT = trinitrotoluene; RDX = cyclotrimethylenetrinitramine; HMX = 1,3,5,7-tetranitro-1,3,5,7-tetrazocane; CHP = Cobalt hydrazine perchlorate; NHP = Nickel hydrazine perchlorate; CHHP = Cobalt hydrazine hydrazinecarboxylate perchlorate. a

Figure 4. Bar chart of the Q values for the known explosives (TNT, RDX, HMX, CHP, NHT, and CHHP), along with the Q values for 1 and 1a.

As shown in Table 1 and Figure 4, 1 and 1a govern predominant detonation properties with Q values of 1.92 kcal·g1 and 2.02 kcal·g-1, respectively, which are even much larger than the conventional explosives, including TNT, RDX, and so on. The D (8.016 km/s for 1 and 8.089 km/s for 1a) and P (34.54 GPa for 1 and 35.01 GPa for 1a) can bear comparison with RDX and HMX, two military high explosives. Noteworthily, it is observed that 1a represents a superior detonation performance than 1, which must be resulted from the water-free structure. The sensitivity experiments for 1 and 1a were explored to test the safety of applying energetic materials (see the Supporting Information). The impact sensitivities (IS) for both compounds are greater than 40 J, whereas the IS for TNT is 15 J under the similar test condition. The friction sensitivity (FS) for 1 exceeds the measurable magnitude 36 kg (360 N), while the FS value of 1a is measured to be 353 N. Also, both compounds are more insensitive to electrostatic discharge than TNT and HMX. Contrast with the known HE-MOFs, 1 and 1a are less sensitive to the external stimulus. It is probably due to the fact that the tight connection between the nitrogen-rich spacers and metallic nodes constructs a solid and insensitive 3D framework. Furthermore, H-bonding interaction between the H2O molecule and ligand in 1 is responsible for the lower friction sensitivity compared with that of 1a. Non-isothermal kinetics analyses of 1 and 1a were performed by differential scanning calorimetric test. The apparent activation energies Ek and Eo, pre-exponential factor A, linear correlation coefficients Rk and Ro for two compounds were

calculated by Kissinger’s and Ozawa–Doyle’s methods, respectively. Ea values derived from the averages of the Ek and Eo are of 39.10 kJ·mol-1 (1) and 39.93 kJ·mol-1 (1a) (see the Supporting Information), revealing the thermo-kinetical inertia in both compounds. Furthermore, the effects of 1 and 1a toward the thermal decomposition for ammonium perchlorate (AP) were studied by DSC measurements and described at the supporting information (Figure S3). It is observed that the exothermal temperature of AP is reduced by nearly 30 oC when AP is mixed with 1 or 1a, respectively. The results illustrate that both compounds can behave as an effective catalyst to boost the thermal decomposition property of AP. In summary, the hydrothermal reaction of H2tza and AgNO3 yields a 3D heptanuclear Ag(I)-MOF, [Ag7(tza)3(Htza)2(H2tza) (H2O)]n (1), which is characterized with good thermostability, insensitivity and heat of detonation compared with traditional energetic materials (TNT and RDX). Subsequently, a new MOF-based high-energy compound 1a, [Ag7(tza)3(Htza)2 (H2tza)]n, has been concisely prepared by the dehydration of 1. Interestingly, owing to the water-free framework, 1a is indicative of a more excellent detonation property and almost identical safety performance with respect to the precursor 1. The outcomes illustrated in this work not only obtain two HEMOFs, but also present an approach to enhance the energetic performance of HE-MOFs.

ASSOCIATED CONTENT Supporting Information.

Figures S1-S3, Tables S1-S5, crystallographic data for 1, CCDC 1878491 (CIF). Experimental details and characterizations

AUTHOR INFORMATION Corresponding author * Xiangyu Liu. E-mail: [email protected] * Sanping Chen. E-mail: [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT


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This work was supported by NSFC (21863009, 21463020, 21673180 and 21727805), the Third Batch of Ningxia Youth Talents Supporting Program (TJGC2018038), the Graduate Innovative Experiment (GIP2018040), and the National First-rate Discipline Construction Project of Ningxia (Chemical Engineering and Technology) (NXYLXK2017A04).

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Table of Contents Synopsis An Ag7-cluster MOF-based energetic material, with remarkable high-energy content, good stability and insensitivity, can be identified as a precursor to transform to its dehydration product which features an enhanced energetic property.

Graphic


6

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99x20mm (600 x 600 DPI)



68x43mm (600 x 600 DPI)


Page 8 of 14

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39x29mm (600 x 600 DPI)



59x43mm (600 x 600 DPI)


Page 10 of 14

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49x18mm (600 x 600 DPI)



44x17mm (600 x 600 DPI)


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33x22mm (600 x 600 DPI)



383x296mm (96 x 96 DPI)


Page 14 of 14

Enhancing energetic performance of multinuclear ... - ACS Publications

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