High‐Capacity Volumetric Methane Storage in Hyper‐Cross‐Linked Porous Polymers via Flexibility Engineering of Building Units

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract Adsorbed natural gas (ANG) storage is emerging as a promising alternative to traditional compressed and liquefied methods. However, its onboard application restricted by low volumetric methane capacity. Flexible porous adsorbents offer potential solution, their dense structures unique gate‐opening effects are well‐suited enhance capacity under high pressures. This study developes series of hyper‐cross‐linked polymers (HCPs) with tunable flexibility modifying the aliphatic chain length in double‐benzene‐ring building blocks, employing cost‐effective external crosslinking approach. The resulting flexible polymer, HCP‐DPP, exhibits pore expansion specific pressures, producing high‐pressure adsorption isotherm behavior. Combined intrinsic skeleton, this feature leads superior performance over rigid counterparts. Notably, HCP‐DPP achieves record‐high total uptake 333 cm 3 STP −3 working 291 at 273 K 100 bar, exceeding U.S. Department Energy (DOE) target 263 . These findings lay foundation for developing advanced practical ANG applications.

Язык: Английский

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3D interpenetrated covalent organic frameworks

Coordination Chemistry Reviews, Год журнала: 2025, Номер 535, С. 216614 - 216614

Опубликована: Март 18, 2025

Язык: Английский

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Single-Crystal X-ray Structures of Homochiral Brønsted Acidic Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Determining the crystal structures of covalent organic frameworks (COFs) with atomic precision is pivotal for uncovering their properties and optimizing functionalities. However, synthesis high-quality single crystals COFs suitable X-ray diffraction analysis, especially chiral (CCOFs), remains a formidable challenge. In this work, we report two three-dimensional (3D) CCOFs synthesized via imine condensation tetrahedral tetraamine tetraaldehydes derived from optically active 1,1′-biphenol phosphoryl chloride or thiophosphoryl chloride. Single varying sizes are obtained through either low-temperature modulation strategy, yielding large up to 100 μm, solvothermal method. The structurally characterized by single-crystal diffraction, achieving resolution 0.90 Å. These isostructural each features 4-fold interpenetrated diamondoid open framework all phosphoric acid groups periodically aligned within tubular helical channels, displaying enhanced Brønsted acidity compared non-immobilized acids. exhibit permanent porosity, chemical resistance in boiling water, 14 M NaOH, 0.1 HCl, thermal stability 400 °C. Notably, these serve as efficient recyclable heterogeneous catalysts asymmetric addition aromatic aldehydes, enantioselective transfer hydrogenation ketimines, three-component direct Mannich reactions involving aldimines cyclic ketones, good high enantioselectivities (up 99.5% ee) that surpass those analogous systems homogeneous catalysts. This work represents first successful demonstration homochiral COFs, paving way in-depth investigations into structure–property relationships processes facilitating design novel functional materials.

Язык: Английский

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Porphyrin-based covalent organic frameworks with undulated layers for efficient photocatalytic CO2 reduction

Science Bulletin, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Язык: Английский

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Thiophene‐Based Bipolar‐Type Covalent Organic Frameworks with Extended π‐Conjugation as Superior Cathode for Lithium‐Ion Batteries

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

Abstract Covalent organic frameworks (COFs) have latterly emerged as a promising platform for devising electrode materials used to acquire high‐performance lithium‐ion batteries (LIBs). However, the preparation of COFs with fast redox kinetics, high‐efficiency utilization active sites, superior stability, and high conductivity remains challenge. Herein, thiophene‐based bipolar‐type (denoted TT‐TPDA‐COF) featuring extended conjugation, rich multiple redox‐active sites (C─S, C─N, C═N), hierarchical micro‐mesoporosity is synthesized. TT‐TPDA‐COF exhibits significantly increased density enhanced electrical compared its corresponding counterpart (Np‐TPDA‐COF). Remarkably, when LIBs cathode, it shows exceptional specific capacity up 309 mA h g −1 at 200 , surpassing that Np‐TPDA‐COF (195 ), energy 714 W kg superb rate property (182 5000 impressive preservation 84.3% after cycles . Additionally, predictable application prototype has been proved by dual‐ion full cells assembled using cathode. Furthermore, storage mechanism comprehensively revealed in/‐ex situ studies theoretical calculations.

Язык: Английский

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Single-Crystal Dynamic Covalent Organic Frameworks for Adaptive Guest Alignments

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 30, 2024

Dynamic 3D covalent organic frameworks (COFs) have shown a concerted structural transformation upon adaptive guest inclusion. However, the origin of conformational mobility and host–guest adaptivity remain conjecture pedal motions revolving imine linkages, often without considering steric hindrance from interwoven frameworks. Here, we present atomic-level observation rotational translational dynamics in single-crystal COF-300 inclusion various molecules, featuring multiple rotamers linkages switchable interframework noncovalent interactions. Specifically, developed diffusion gradient transimination protocol to facilitate growth COF single crystals, enabling high-resolution X-ray diffraction analysis. We uncovered metastable low-symmetry intermediate phases contracted expanded during evolution. identified torsion angles terephthalaldehyde diimine motifs that switch anti-periplanar syn-periplanar/anticlinal conformations. Moreover, linkage were concurrent with tetraphenylmethane units, which tend form quadruple phenyl embrace. Such allows adapt such as alcohols, esters, phenols, diols, double linear, herringbone, zigzag chains, triple helix, tubular alignments. Quantitative energy analyses revealed dynamic structure transformations are not arbitrary but follow specific pathways resemble protein folding. The work is paving way developing robust, dynamic, crystalline molecular sponges for studying condensed liquids need further crystallization.

Язык: Английский

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