Modifying the separator is considered as an effective strategy for achieving high performance lithium-sulfur (Li-S) batteries. However, most modification layers are excessively thick, with catalytic active sites primarily located within the material's interior. This configuration severely impacts Li transport and the efficient catalytic conversion of polysulfides.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Targeted at organic dye pollutants, a stable HOF was combined with an alginate (SA) hydrogel to enhance the affinity for cationic dyes. The as-obtained HOF@SA membrane (weight ratio: 1/1) shows a high adsorption capacity (729.21 mg g), adsorption selectivity and good recycling performance towards methylene blue.
View Article and Find Full Text PDFAchieving efficient xenon/krypton (Xe/Kr) separation in emerging hydrogen-bonded organic frameworks (HOFs) is highly challenging because of the lack of gas-binding sites on their pore surfaces. Herein, we report the first microporous HOF (HOF-FJU-168) based on hydrogen-bonded helical chains, which prevent self-aggregation of the pyrene core, thereby preserving open pyrene sites on the pore surfaces. Its activated form, HOF-FJU-168a is capable of separating Xe/Kr under ambient conditions while achieving an excellent balance between adsorption capacity and selectivity.
View Article and Find Full Text PDFThe separation of propylene (CH) and propane (CH) is of great significance in the chemical industry, which poses a challenge due to their almost identical kinetic diameters and similar physical properties. In this work, we synthesized an ultramicroporous flexible hydrogen-bonded organic framework (named HOF-FJU-106) by using molecule 2,3,6,7-tetra (4-cyanophenyl) tetrathiafulvalene (TTF-4CN). The formation of the dimer causes the TTF-4CN molecular to bend and weaken π-stacked interactions, coupled with the flexibility of C≡N H-C hydrogen bonds, which leads to reversible conversion between open and closed frameworks through the mutual slip of adjacent layers/columns under activation and stimulation of gas molecules.
View Article and Find Full Text PDFMetal-organic framework (MOF) heterostructures with hybrid architectures and abundant functional sites possess great potential applications in advanced information security, yet still suffer from the harsh stimuli mechanisms with restrained emission control. Herein, the differentiated design strategy on intra-ligand charge transfer is first reported to realize smart-responsive multicolor MOF heterostructures as robust anticounterfeiting labels. Designed similar MOF blocks with the differentiated intra-ligand charge transfer are integrated via time-dependent epitaxial growth to form multicolor MOF heterostructures.
View Article and Find Full Text PDFRecently B←N organic frameworks (BNFs) have gained substantial attention owing to their unique dative bond energy, which imparts them with specialized functionalities across a broad spectrum of applications. Despite previous reports on BNFs with permanent porosity, research endeavors towards three-dimensional (3D) BNFs with similar properties are scarce, with no report of robust 3D BNFs featuring permanent porosity to date. Herein, electrostatic complementary strategy is proposed to construct the first example of 3D robust and microporous BNF, BNF-100, featuring a reo topology with 8-connected sandwich nodes assembled via dative B←N bonds.
View Article and Find Full Text PDFReticular chemistry and pore engineering have garnered significant advancements in metal-organic frameworks and covalent organic frameworks, leveraging robust metal-coordination and covalent bonds. However, these achievements remain elusive in hydrogen-bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen-bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF-FJU-99 and HOF-FJU-100, with distinct pore environments.
View Article and Find Full Text PDFDevelopment of highly porous and robust hydrogen-bonded organic frameworks (HOFs) for high-pressure methane and hydrogen storage remains a grand challenge due to the fragile nature of hydrogen bonds. Herein, we report a strategy of constructing the double-walled framework to target highly porous and robust HOF (ZJU-HOF-5a) for extraordinary CH and H storage. ZJU-HOF-5a features a minimized twofold interpenetration with double-walled structure, in which multiple supramolecular interactions are existed between the interpenetrated walls.
View Article and Find Full Text PDFMass transfer of bulky molecules, ., bioenzymes, particularly for cross-scale multibiomolecules, imposes serious challenges for microporous metal-organic frameworks (MOFs). Here, we create a hierarchically porous MOF heterostructure featuring highly region-ordered micro-, meso-, and macro-pores by growing a microporous ZIF-8 shell onto a hollow Prussian blue core through an epitaxial growth strategy.
View Article and Find Full Text PDFMolecular sieving of propylene (CH) from propane (CH) is highly demanded for CH purification. However, delicate control over aperture size to achieve both high CH uptake and CH/CH selectivity with low cost remains a significant challenge. Herein, a green and scalable approach is reported for preparing an isomeric CALF-20 adsorbent, termed as NCU-20, using water as the only solvent with a cost of $10 per kilogram.
View Article and Find Full Text PDFFlexible behavior is one of the most fascinating features of hydrogen-bonded organic frameworks (HOFs), which represent an emerging class of porous materials that are self-assembled H-bonding between organic building units. Due to their unique flexibility, HOFs can undergo structural changes or transformations in response to various stimuli (physical or chemical). Taking advantage of this unique structural feature, flexible HOFs show potential in multifunctional applications such as gas storage/separation, molecular recognition, sensing, proton conductivity, biomedicine, While some other flexible porous materials have been extensively studied, the dynamic behavior of HOFs remains relatively less explored.
View Article and Find Full Text PDFThe effective separation of aromatic and aliphatic hydrocarbons remains a notable challenge in the petrochemical industry. Herein, we report a self-healing three-dimensional B ← N-based hydrogen-bonded organic framework (HOF), BN-HOF-1, constructed from discrete B ← N inclusive dimers through weak C-H···F and C-H···N hydrogen-bonding interactions. To make use of the specific recognition of the B ← N inclusive dimers for the toluene molecules and the reversible ad/desorption nature of this novel HOF, BN-HOF-1 can exclusively recognize and separate toluene from the mixtures of toluene-methylcyclohexane, thus generating 99.
View Article and Find Full Text PDFLithium-sulfur (Li-S) batteries have attracted significant attention in the realm of electronic energy storage and conversion owing to their remarkable theoretical energy density and cost-effectiveness. However, Li-S batteries continue to face significant challenges, primarily the severe polysulfides shuttle effect and sluggish sulfur redox kinetics, which are inherent obstacles to their practical application. Metal-organic frameworks (MOFs), known for their porous structure, high adsorption capacity, structural flexibility, and easy synthesis, have emerged as ideal materials for separator modification.
View Article and Find Full Text PDFThe efficient separation of CH from CH/CO or CH/CO/CH mixtures is crucial for achieving high-purity CH (>99%), essential in producing contemporary commodity chemicals. In this report, we present ZNU-12, a metal-organic framework with space-partitioned pores formed by inorganic fluorinated anions, for highly efficient CH/CO and CH/CO/CH separation. The framework, partitioned by fluorinated SiF anions into three distinct cages, enables both a high CH capacity (176.
View Article and Find Full Text PDFSeparating acetylene from carbon dioxide is important but highly challenging due to their similar molecular shapes and physical properties. Adsorptive separation of carbon dioxide from acetylene can directly produce pure acetylene but is hardly realized because of relatively polarizable acetylene binds more strongly. Here, we reverse the CO and CH separation by adjusting the pore structures in two isoreticular ultramicroporous metal-organic frameworks (MOFs).
View Article and Find Full Text PDFSince ethylene (CH) is important feedstock in the chemical industry, developing economical and energy-efficient adsorption separation techniques based on ethane (CH)-selective adsorbents to replace the energy-intensive cryogenic distillation is highly demanded, which however remains a daunting challenge. While previous anionic boron cluster hybrid microporous materials display CH-selective features, we herein reported that the incorporation of a neutral -carborane backbone and aliphatic 1,4-diazabicyclo[2.2.
View Article and Find Full Text PDFThe development of porous materials with flexible-robust characteristics shows some unique advantages to target high performance for gas separation, but remains a daunting challenge to achieve so far. Herein, we report a carboxyl-based hydrogen-bonded organic framework (ZJU-HOF-8a) with flexible-robust porosity for efficient purification of natural gas. ZJU-HOF-8a features a four-fold interpenetrated structure with dia topology, wherein abundant supramolecular entanglements are formed between the adjacent subnetworks through weak intermolecular hydrogen bonds.
View Article and Find Full Text PDFDirectional control of photon transport at micro/nanoscale holds great potential in developing multifunctional optoelectronic devices. Here, the switchable anisotropic/isotropic photon transport is reported in a double-dipole metal-organic framework (MOF) based on radical-controlled energy transfer. Double-dipole MOF microcrystals with transition dipole moments perpendicular to each other have been achieved by the pillared-layer coordination strategy.
View Article and Find Full Text PDFHydrogen-bonded organic frameworks (HOFs) are a new class of crystalline porous materials that are formed through the interconnection of organic or metal-organic building units intermolecular hydrogen bonds. The remarkable flexibility and reversibility of hydrogen bonds, coupled with the customizable nature of organic units, endow HOFs with mild synthesis conditions, high crystallinity, solvent processability, and facile self-healing and regeneration properties. Consequently, these features have garnered significant attention across various fields, particularly in the realm of membrane separation.
View Article and Find Full Text PDFTautomers coexisting in an equilibrium system have significant potential for regulating luminescent properties because of their structural differences. However, separating and stabilizing tautomers at room temperature is a considerable challenge. In this study, it is found that hydrogen-bonded organic frameworks (HOFs) composed of Br anions can effectively separate and stabilize two proton-transfer tautomers of triarylformamidinium bromide: namely, the nitrogen cation (BA-N) and carbon cation (BA-C).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2024