RESUMEN
Superstructures with complex hierarchical spatial configurations exhibit broader structural depth than single hierarchical structures and the associated broader application prospects. However, current preparation methods are greatly constrained by cumbersome steps and harsh conditions. Here, for the first time, a concise and efficient thermally responsive dynamic synthesis strategy for the preparation of multidimensional complex superstructures within soluble covalent organic networks (SCONs) with tunable morphology from 0D hollow supraparticles to 2D films is presented. Mechanism study reveals the thermally responsive dynamic "cleavage-remodeling" characteristics of SCONs, synthesized based on the unique bilayer structure of (2.2)paracyclophane, and the temperature control facilitates the process from reversible solubility to reorganization and construction of superstructures. Specifically, during the process, the oil-water-emulsion two-phase interface can be generated through droplet jetting, leading to the preparation of 0D hollow supraparticles and other bowl-like complex superstructures with high yield. Additionally, by modulating the volatility and solubility of exogenous solvents, defect-free 2D films are prepared relying on an air-liquid interface. Expanded experiments further confirm the generalizability and scalability of the proposed dynamic "cleavage-remodeling" strategy. Research on the enrichment mechanism of guest iodine highlights the superior kinetic mass transfer performance of superstructural products compared to single-hierarchical materials.
RESUMEN
As one of the most attractive methods for the synthesis of ordered hierarchically porous crystalline materials, the soft-template method has not appeared in covalent organic frameworks (COFs) due to the incompatibility of surfactant self-assembly and guided crystallization process of COF precursors in the organic phase. Herein, we connect the soft templates to the COF backbone through ionic bonds, avoiding their crystallization incompatibilities, thus introducing an additional ordered arrangement of soft templates into the anionic microporous COFs. The ion exchange method is used to remove the templates while maintaining the high crystallinity of COFs, resulting in the construction of COFs with ordered hierarchically micropores/mesopores, herein named OHMMCOFs (OHMMCOF-1 and OHMMCOF-2). OHMMCOFs exhibit significantly enhanced functional group accessibility and faster mass transfer rate. The extrinsic porosity can be adjusted by changing the template length, concentration, and ratio. Cationic guanidine-based COFs (OHMMCOF-3) are also constructed using the same method, which verifies the scalability of the soft-template strategy. This work provides a path for constructing ordered and tunable extrinsic porosity in COFs with greatly improved mass transfer efficiency and functional group accessibility.
RESUMEN
The majority of COFs synthesized using current methods exist as insoluble powders, which is unfavorable for processing and molding and greatly limits their practical applications. The syntheses of solution-processable or soluble COFs are challenging but hold immense promise and potential. Herein, for the first time, we have developed a simple and high-efficiency solvothermal-treated unit exchange approach to convert insoluble COF powders into smaller, highly soluble COFs via a hydrogen bond-assisted strategy. Due to the enhanced backbone-solvent hydrogen-bonding interactions between COFs and protic solvents and the effect of grain size reduction, the COFs after unit exchange can be easily dissolved in various protic solvents while remaining as insoluble powders in nonprotic solvents. The obtained soluble COFs exhibit remarkable fluorescence quenching upon detection of iodine in aqueous solution, with a detection limit as low as 75 nM, and can be fabricated into membranes for the efficient treatment of iodine-contaminated solutions.
RESUMEN
Developing crystalline porous materials with highly efficient CO2 selective adsorption capacity is one of the key challenges to carbon capture and storage (CCS). In current studies, much more attention has been paid to the crystalline and porous properties of crystalline porous materials for CCS, while the defects, which are unavoidable and ubiquitous, are relatively neglected. Herein, for the first time, we propose a monomer-symmetry regulation strategy for directional defect release to achieve in situ functionalization of COFs while exposing uniformly distributed defect-aldehyde groups as functionalization sites for selective CO2 capture. The regulated defective COFs possess high crystallinity, good structural stability, and a large number of organized and functionalized aldehyde sites, which exhibit one of the highest selective separation values of all COF sorbing materials in CO2/N2 selective adsorption (128.9 cm3/g at 273 K and 1 bar, selectivity: 45.8 from IAST). This work not only provides a new strategy for defect regulation and in situ functionalization of COFs but also provides a valuable approach in the design and preparation of new adsorbents for CO2 adsorption and CO2/N2 selective separation.
RESUMEN
Compared to the current mainstream rigid covalent organic frameworks (COFs) linked by imine bonds, flexible COFs have certain advantages of elasticity and self-adaptability, but their construction and application are greatly limited by the complexity in synthesis and difficulty in obtaining regular structure. Herein, we reported for the first time a series of flexible amine-linked COFs with high crystallinity synthesized by formic acid with unique catalytic and reductive bifunctional properties, rather than acetic acid, the most common catalyst for COF synthesis. The reaction mechanism was demonstrated to be a synchronous in situ reduction during the formation of imine bond. The flexibilities of the products endow them with accommodative adaptability to guest molecules, thus increasing the adsorption capacities for nitrogen and iodine by 27 % and 22 %, respectively. Impressively, a novel concept of flexibilization degree was proposed firstly, which provides an effective approach to rationally measure the flexibility of COFs.
RESUMEN
The separation and recovery of key nuclides such as uranium and plutonium from effluents related to nuclear industry is of great significance for alleviating the shortage of nuclear energy resources and protecting the environment and human health. However, the high temperature, strong acidity and radioactivity of the nuclear effluents pose a severe challenge to the separation materials used in such conditions. The diversity of structure, flexibility of design, and excellent physicochemical stability of covalent organic framework materials (COFs) provide the possibility for the directional design and preparation of adsorbents for use under harsh conditions. Herein, three COFs with similar structure, different pore sizes and connecting modules were synthesized. The ingenious structure predesign enables Dp-COF to have three carboxyl groups oriented toward the pore center and laid out in appropriate spatial positions, which builds hydrogen-bonding bridges between carboxycarbonyl and hydroxyl groups, and thus constructs for the first time a unique COF material with a double-ring pore. The inner pore size of the "double-ring" is slightly larger than the diameter of uranyl hydrate, which leads to a size-matching adsorption of uranium by Dp-COF, thus greatly reducing the effect of protonation. Even in the simulated spent fuel reprocessing liquid with pH = 1.0, the adsorption capacity of Dp-COF for uranium can reach 66.3 mg g-1, and the adsorption capacity reaches 317.3 mg g-1 at pH = 4.5, which is very rare among the reported COFs. More excitingly, the removal rate for uranium reaches up to an unprecedented 99.8% due to the size-matching effect, more than any analogous adsorbents. This study not only proposes new ideas for the design and regulation of the microscopic configuration of COF materials, but also provides an alternative approach for the preparation of efficient uranium adsorbents.
