Covalent organic frameworks (COFs) are the emerging type of organic crystalline porous materials, prepared through reticular chemistry with building blocks featuring light elements (such as C, H, O, N, or B atoms), and connected through the covalent bond and extended into two or three dimensions. In the past few years, COFs have attracted attention for their interesting properties, including high-order porosity, structural versatility, facile surface modification, and high thermal and chemical stabilities. Accordingly, COFs are potential platforms for diverse practical implementations, including gas separation and storage, heterogeneous catalysis, chemical sensing, luminescence, electronic devices, drug delivery, and energy storage and conversion. This Review provides the overview of the design strategies and synthetic methodologies that have been used widely for the preparation of COFs, and also summarizes selected examples of their applications.

Covalent organic frameworks: Design principles, synthetic strategies, and diverse applications

In this review, we discuss the progress in the preparation methods and diverse applications for covalent triazine frameworks, hypercrosslinked polymers, covalent organic frameworks, and conjugated microporous polymers. 

Advances in porous organic polymers: syntheses, structures, and diverse applications

Solid-State Chemical Transformations to Enhance Gas Capture in Benzoxazine-Linked Conjugated Microporous Polymers

In this study, two different types of hybrid porous organic polymers (POPs), polyhedral oligomeric silsesquioxane tetraphenylpyrazine (POSS-TPP) and tetraphenylethene (POSS-TPE), were successfully synthesized through the Friedel−Crafts polymerization of tetraphenylpyrazine (TPP) and tetraphenylethene (TPE), respectively, with octavinylsilsesquioxane (OVS) as node building blocks, in the presence of anhydrous FeCl3 as a catalyst and 1,2-dichloroethane at 60 °C. Based on N2 adsorption and thermogravimetric analyses, the resulting hybrid porous materials displayed high surface areas (270 m2/g for POSS-TPP and 741 m2/g for POSS-TPE) and outstanding thermal stabilities. Furthermore, as-prepared POSS-TPP exhibited a high carbon dioxide capacity (1.63 mmol/g at 298 K and 2.88 mmol/g at 273 K) with an excellent high adsorption capacity for iodine, reaching up to 363 mg/g, compared with the POSS-TPE (309 mg/g).

Multifunctional Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Porous Materials for CO2 Uptake and Iodine Adsorption.

In this study, we prepared a series of conjugated microporous polymers (CMPs) through Sonogashira-Hagihara cross-couplings of a tetrabenzonaphthalene (TBN) monomer with pyrene (Py), tetraphenylethylene (TPE), and carbazole (Car) units and examined their chemical structures, thermal stabilities, morphologies, crystallinities, and porosities. TBN-TPE-CMP possessed a high surface area (1150 m2 g-1) and thermal stability (Td10 = 505 °C; char yield = 68 wt %) superior to those of TBN-Py-CMP and TBN-Car-CMP. To improve the conductivity of the TBN-CMP materials, we blended them with highly conductive single-walled carbon nanotubes (SWCNTs). Electrochemical measurements revealed that the TBN-Py-CMP/SWCNT nanocomposite had high capacitance (430 F g-1) at a current density of 0.5 A g-1 and outstanding capacitance retention (99.18%) over 2000 cycles; these characteristics were superior to those of the TBN-TPE-CMP/SWCNT and TBN-Car-CMP/SWCNT nanocomposites.

High-Performance Supercapacitor Electrodes Prepared From Dispersions of Tetrabenzonaphthalene-Based Conjugated Microporous Polymers and Carbon Nanotubes.

Ultrastable luminescent hybrid microporous polymers based on polyhedral oligomeric silsesquioxane for CO2 uptake and metal ion sensing

Research Progress of Nitrate Ester Binders

Safety concerns remain a bottleneck for the application of 2,4,6,8,10,12-hexanitro- 2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)/1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) cocrystal. Melamine–formaldehyde (MF) resin was chosen to fabricate CL-20/HMX cocrystal-based core–shell composites (CH@MF composites) via a facile in situ polymerization method. The resulted CH@MF composites were comprehensively characterized, and a compact core–shell structure was confirmed. The effects of the shell content on the properties of the composites were explored as well. As a result, we found that, except for CH@MF–2 with a 1% shell content, the increase in shell content led to a rougher surface morphology and more close-packed structure. The thermal decomposition peak temperature improved by 5.3 °C for the cocrystal enabled in 1.0 wt% MF resin. Regarding the sensitivity, the CH@MF composites exhibited a significantly reduced impact and friction sensitivity with negligible energy loss compared with the raw cocrystal and physical mixtures due to the cushioning and insulation effects of the MF coating. The formation mechanism of the core–shell micro-composites was further clarified. Overall, this work provides a green, facile and industrially potential strategy for the desensitization of energetic cocrystals. The CH@MF composites with high thermal stability and low sensitivity are promising to be applied in propellants and polymer-bonded explosive (PBX) formulations.

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Fabrication of CL-20/HMX Cocrystal@Melamine–Formaldehyde Resin Core–Shell Composites Featuring Enhanced Thermal and Safety Performance via In Situ Polymerization

Molecular Dynamics Simulation on Ε-Cl-20 Based Pbxs with Chain-Extended Poly(3,3-Bis(Azidomethyl)Oxetane)

Energetic Metal Organic Frameworks (EMOFs) have been a hotspot of research on solid propellants in recent years. In this paper, research on the application of EMOFs-based burning rate catalysts in solid propellants was reviewed and the development trend of these catalysts was explored. The catalysts analyzed included monometallic organic frameworks-based energetic burning rate catalysts, bimetallic multifunctional energetic burning rate catalysts, carbon-supported EMOFs burning rate catalysts, and catalysts that can be used in conjunction with EMOFs. The review suggest that monometallic organic frameworks-based burning rate catalysts have relatively simple catalytic effects, and adding metal salts can improve their catalytic effect. Bimetallic multifunctional energetic burning rate catalysts have excellent catalytic performance and the potential for broad application. The investigation of carbon-supported EMOFs burning rate catalysts is still at a preliminary stage, but their preparation and application have become a research focus in the burning rate catalyst field. The application of catalysts that can be compounded with EMOFs should be promoted. Finally, environmental protection, high energy and low sensitivity, nanometerization, multifunctional compounding and solvent-free are proposed as key directions of future research. This study aims to provide a reference for the application of energetic organic burning rate catalysts in solid propellants.

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Ni-Yun Liu

Papers

Ultrastable luminescent hybrid microporous polymers based on polyhedral oligomeric silsesquioxane for CO2 uptake and metal ion sensing

Research Progress of Nitrate Ester Binders

Fabrication of CL-20/HMX Cocrystal@Melamine–Formaldehyde Resin Core–Shell Composites Featuring Enhanced Thermal and Safety Performance via In Situ Polymerization

Molecular Dynamics Simulation on Ε-Cl-20 Based Pbxs with Chain-Extended Poly(3,3-Bis(Azidomethyl)Oxetane)

Research progress of EMOFs-based burning rate catalysts for solid propellants