Facile synthesis and superior properties of a nitrogen-rich energetic Zn-MOF with a 2D azide-bridged bilayer structure

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Abstract
Exploring the facile synthesis of Pb-free energetic metal–organic frameworks (EMOFs) with both high nitrogen content and high thermostability is a significant but challenging task in the field of MOF-based green energetic materials. Herein, a new EMOF, [Zn2(atz)3(N3)]n (atz = 5-amino-1H-tetrazole), has been synthesized by simply using a commercial ligand (atz) under mild conditions. A probable mechanism for the formation of azide groups in the product has been proposed, in which the fraction of C–N and N–N bonds in atz is the key. The X-ray single crystal structure analysis reveals the EMOF's unique graphene-like and azide-group-bridged 2D bilayer structure with gourd-type micropores. More impressively, the EMOF shows a high nitrogen content of 59.33% and superior thermostability of up to 362 °C, both among the best of existing EMOFs. In addition, detonation property calculations and sensitivity tests have been carried out, which demonstrate its high-energy and low-sensitivity features. Moreover, [Zn2(atz)3(N3)]n shows the ability to accelerate the thermal decomposition of ammonium perchlorate (AP) and hexanitrohexaazaisowurtzitane (CL-20), making it a potential combustion promoter for green and insensitive propellants.
Funding Information
  • National Natural Science Foundation of China (22105156)
  • National Natural Science Foundation of China (22175139)

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