A 2D nickel-based energetic MOFs incorporating 3,5-diamino-1,2,4-triazole and malonic acid: Synthesis, crystal structure and thermochemical study

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Highlights

Abstract

A new energetic MOFs, {[Ni2(C2H5N5)2(C3H2O4)2(H2O)]·3H2O}n (Hdatrz (C2H5N5) = 3,5-diamino-1,2,4-triazole, H2mal (C3H4O4) = malonic acid), has been synthesized and characterized by element analysis, chemical analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analysis confirmed that the compound featured a 2D layer structure with dinuclear Ni(II) unit. Thermal analysis demonstrated that the compound after dehydration have good thermostability with decomposition temperature up to 633 K. The non-isothermal kinetics for the compound was studied by Kissinger’s and Ozawa’s methods. The Arrhenius equation of initial thermal decomposition process of compound can be expressed as ln k = 55.89  332.01 × 103/RT. Furthermore, a reasonable thermochemical cycle was designed based on the preparation reaction of the compound, and standard molar enthalpy of dissolution of reactants and products were measured by RD496-2000 calorimeter. Finally, the standard molar enthalpy of formation of the compound was determined to be −(2766.3 ± 2.3) kJ · mol−1 in accordance with Hess’s law. In addition, the specific heat capacity of the compound at T = 298.15 K was determined to be 1.42 ± 0.11 J · K−1 · g−1 by RD496-2000 calorimeter.

Introduction

Metal–organic frameworks (MOFs) have attracted an extensive interest because of their stable architectures and potential applications in gas storage [1], chemical separation [2], heterogeneous catalysis [3], sensing [4], sorption [5], drug delivery [6], and so on. Particularly, MOFs could also be potential energetic materials because of their high densities and high heats of detonation. For example, Hope-Weeks reported two 1D MOFs [Ni(NH2NH2)5(ClO4)2]n and [Co(NH2NH2)5(ClO4)2]n with linear polymeric structures, which were regarded as possible the most powerful metal-based energetic materials known to date [7]. In recent years, our research group continues focus on the chemistry of triazole derivatives and carboxylic acid, which can provide us energetic MOFs with high nitrogen and high oxygen as ingredients for propellants and explosives [8], [9]. As one of triazole derivatives, 3,5-diamino-1,2,4-triazole, is a significant energetic intermediate with nitrogen content 70.67%, and it have been studied and produced some energetic compounds [10], [11]. Malonic acid is a common and useful ligand for constructing crystalline architectures due to its flexible, proton donating and accepting capabilities for hydrogen bonding via the oxygen atoms of its carboxylate groups. Nickle (II) exhibits a good ability when coordinating with different kinds of ligand, and is more environmental friendly compared with the toxic heavy metal ions as lead and mercury.

The datum of the standard molar enthalpy of formation and specific heat capacity play important role in theoretical study, application development and industrial production of a compound as a basis of theoretical analysis [12], [13], [14]. In spite of that, to our best knowledge, there is little reliable experimental data available for such compounds.

Herein, in this paper, we report the synthesis, crystal structure, thermal analysis, standard molar enthalpy of formation and specific heat capacity of the title MOFs, {[Ni2(C2H5N5)2(C3H2O4)2(H2O)]·3H2O}n (1), which will lay the foundation for further energetic research and application.

Section snippets

Materials, equipments and analytical methods

All chemicals involved were acquired from commercial sources at analytical grade and used without further purification, detailed information is provided in table 1. Elemental analysis was carried out with an Elementar Vario EL III CHNOS analyzer. The chemical compositions of the sample were determined by EDTA titration for Ni2+. IR spectra were recorded with a Bruker FTTR instrument as KBr pellets (4000 to 400) cm−1. Differential scanning calorimetry (DSC) and thermogravimetric measurements were

Description of the structure

Singe-crystal X-ray diffraction reveals that the asymmetric unit structure of 1 consists of crystallographically independent two Ni(II) ions and figure 2a depicts the coordination environment around Ni(II). The five-coordinated Ni1 ion exhibits a distorted square pyramidal geometry formed by two nitrogen atoms from two Hdatrz ligands, two oxygen atoms from one mal2− ligand and one oxygen atom from another mal2− ligand. The six-coordinated Ni2 ion is of a distorted octahedron coordination

Conclusion

In summary, an energetic MOFs, {[Ni2(C2H5N5)2(C3H2O4)2(H2O)]·3H2O}n, which exhibits a 2D layer structure with polymeric dinuclear unit, has been synthesized and characterized. The compound after dehydration possesses high thermal stability up to T = 633 K. The Arrhenius equation, derived from non-isothermal kinetics analysis, is ln k = 55.89  332.01 × 103/RT. Through an appropriate thermochemical cycle, the standard molar enthalpy of formation of the compound has been obtained. The large value of the

Acknowledgements

We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Grant Nos. 21127004, 21173168 and 21203149), Doctoral Fund for New Teachers of Ministry of Education of China (No. 20116101120022).

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