Highly Thermostable and Insensitive Energetic Hybrid Coordination Polymers Based on Graphene Oxide–Cu(II) Complex

Abstract

New highly energetic coordination polymers (ECPs), based on the graphene oxide (GO)-copper(II) complex, have been synthesized using 5,5′-azo-1,2,3,4-tetrazole (TEZ) and 4,4′-azo-1,2,4-triazole (ATRZ), as linking ligands between GO-Cu layers. The molecular structures, sensitivity, and detonation performances of these ECPs were determined. It was shown that these energetic nanomaterials are insensitive and highly thermostable, due to high heat and impact dissipation capacity of GO sheets. In particular, the GO-TEZ-Cu(II) ECP shows low sensitivity to impact and electrostatic discharge (I m = 21 J; ESD of 1995 mJ) and has a comparable detonation performance to RDX. Also, our novel GO/Cu(II)/ATRZ hybrid ECP GO-Cu(II)-ATRZ ECP exhibits high density (2.85 g•cm −3 ), remarkably high thermostability (T p = 456 °C), and low sensitivity (I m > 98 J; ESD of 1000 mJ). The latter material has a calculated detonation velocity of 7082 m•s −1 , which is slightly higher than that of energetic ATRZ-Cu(II) 3D MOF and higher than one of the top thermostable explosives HNS (T p = 316 °C; 7000 m s −1 ).

An Improved Metal‐to‐Ligand Charge Transfer Mechanism for Photocatalytic Hydrogen Evolution

“…Compared with the C1ss pectrum of CNNS-COOH, the peak from 286.0 to 290.0 eV was broadened and ap eak at 287.3 eV was observed in the CNNS-BTEC-Cu-3 sample, confirming the presenceo fC -O-Cub onds. [19] Additionally,a na pparent negative shift waso bserved in the O1ss pectrum of CNNS-BTEC-Cu-3 ( Figure S4), which can be attributed to the coordinationi nteraction with lesselectronegative copper(II). No significant shift was observed in the N1ss pectrum of CNNS-BTEC-Cu-3 ( Figure S5), indicating that Na toms in CNNS-COOH did not participate in the coordination reaction.…”

“…Fitted C 1s XPS spectra of CNNS‐COOH (Figure S3) and CNNS‐BTEC‐Cu‐3 (Figure D) clearly revealed the presence of oxygen‐containing functional groups in both samples. Compared with the C 1s spectrum of CNNS‐COOH, the peak from 286.0 to 290.0 eV was broadened and a peak at 287.3 eV was observed in the CNNS‐BTEC‐Cu‐3 sample, confirming the presence of C‐O‐Cu bonds . Additionally, an apparent negative shift was observed in the O 1s spectrum of CNNS‐BTEC‐Cu‐3 (Figure S4), which can be attributed to the coordination interaction with less‐electronegative copper(II).…”

Amine Functionalized Metal–Organic Framework Coordinated with Transition Metal Ions: d–d Transition Enhanced Optical Absorption and Role of Transition Metal Sites on Solar Light Driven H2 Production

“…The peak intensity related to –NH 2 group is greatly decreased which indicates effective coordination of transition metal ions through –NH 2 group of Ti‐MOF. Very importantly, the new binding energy peaks appeared at 400.5, 400.28, and 401.1 eV in the case of Co 2+ , Ni 2+ , and Cu 2+ coordinated MOFs are related to the positively charged amino group (–NH 2 + ) . This can be attributed to the formation of quaternary valence –NH 2 + by successful donation of non‐bonded electrons of –NH 2 group to M 2+ ions for the effective coordination, as a result –NH 2 becomes as quaternary valence (–NH 2 + ).…”

Metal‐Organic Frameworks/Graphene‐Based Materials: Preparations and Applications

“…It is certain that the combination of graphene‐based materials and MOFs is an effective strategy to offer suitable electrode materials for supercapacitors. Although MOFs are believed to be a promising electrode material on account of their crystallinity and porosity, the low capacitance and inferior electron mobility within traditional MOF‐based supercapacitors have prevented the electrodes from displaying their best performance . In contrast, the assembly of graphene‐based materials overcame these shortcomings and brought the hybrid materials better abilities .…”