RESUMEN
Developing MOF-based catalysts with superior catalytic properties for the thermal decomposition of cyclotrimethylenetrinitramine (RDX) is significant for the application of novel and efficient combustion catalysts oriented to RDX-based propellants with excellent combustion performance. Herein, micro-sized Co-ZIF-L with a star-like morphology (SL-Co-ZIF-L) was found to exhibit unprecedented catalytic capability for the decomposition of RDX, which can lower the decomposition temperature of RDX by 42.9 °C and boost the heat release by 50.8%, superior to that of all the ever-reported MOFs and even ZIF-67, which has similar chemical composition but a much smaller size. In-depth mechanism study from both experimental and theoretical views reveals that the weekly interacted 2D layered structure of SL-Co-ZIF-L could activate the exothermic C-N fission pathway for the decomposition of RDX in the condensed phase, thus reversing the commonly advantageous N-N fission pathway and promoting the decomposition process in the low-temperature stage. Our study reveals the unusually superior catalytic capability of micro-sized MOF catalysts and sheds light on the rational structure design of catalysts used in micromolecule transformation reactions, typically the thermal decomposition of energetic materials.
RESUMEN
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.
RESUMEN
Efficient photocatalytic conversion of CO2 into energy-rich chemicals is of great significance for both environmental conservation and alleviating the energy crisis. However, convenient synthesis of low-cost, durable and eco-friendly photocatalysts with a novel morphology or structure for highly selective photocatalytic CO2 reduction remains a challenge. Herein, Co3O4 hierarchical nanosheets were synthesized by calcination of novel cobalt metal-organic framework (MOF) nanosheets prepared by a facile oil bath method. In such Co MOF nanosheets, 1,4-naphthalenedicarboxylic acid was chosen as the organic linker, rather than the commonly used 2-methylimidazole for ZIF-67. After thermal treatment in air, the obtained Co3O4 inherited the 2D morphology of its MOF template and evolved into hierarchical nanosheets which were composed of small nanoparticles. Benefiting from the large surface area, abundant mesoporous structure and good capability towards the separation and transfer of photo-generated charge carriers induced by less internal oxygen vacancies, the Co3O4 hierarchical nanosheets showed a CO generation rate of 39.70 µmol h-1 in visible-light photocatalytic CO2 reduction, which was superior to that of Co3O4 nanoparticles and commercial Co3O4. What's more, a CO selectivity of 77.3% was achieved, which is among the highest of cobalt-based spinel oxide photocatalysts for CO2 conversion.