Ionic Liquid-Accelerated Growth of Covalent Organic Frameworks with Tunable Layer-Stacking.

Layer-stacking behaviors are crucial for two-dimensional covalent organic frameworks (2D COFs) to define their pore structure, physicochemical properties, and functional output. So far, fine control over the stacking mode without complex procedures remains a grand challenge. Herein, we proposed a "key-cylinder lock mimic" strategy to synthesize 2D COFs with a tunable layer-stacking mode by taking advantage of ionic liquids (ILs). The staggered (AB) stacking (unlocked) COFs were exclusively obtained by incorporating ILs of symmetric polarity and matching molecular size; otherwise, commonly reported eclipsed (AA) stacking (locked) COFs were observed instead. Mechanistic study revealed that AB stacking was induced by a confined interlocking effect (CIE) brought by anions and bulky cations of the ILs inside pores ("key" and "cylinder", respectively). Excitingly, this strategy can speed up production rate of crystalline powders (e.g., COF-TAPT-Tf@BmimTf2N in merely 30 minutes) under mild reaction conditions. This work highlights the enabling role of ILs to tailor the layer stacking of 2D COFs and promotes further exploration of their stacking mode-dependant applications.

Aqueous Sol-Gel Synthesis and Shaping of Covalent Organic Frameworks.

The intrinsic fragility and insoluble nature of covalent organic frameworks (COFs) have strongly impeded their processability for practical applications. Herein, an aqueous-based sol-gel synthetic strategy is reported for the synthesis and shaping of COFs with task-specific applications that satisfy the principles of green chemistry for gram-scale production of crystalline materials. Our successful approach involves three pivotal aspects: the "prodrug mimic" design of water-soluble monomers, the utilization of hydrolyzable bonds, and the manipulation of reaction kinetics. The generality of the method is demonstrated by the successful preparation of representative high-surface area two-dimensional (2D) COFs with several commonly used amines. By virtue of this strategy, a COF colloidal dispersion is achieved and can be formulated into processable fluids, structured films, and COF monoliths. Remarkably, the obtained lightweight (∼0.020 g cm-3) and robust aerogels displayed outstanding adsorption capacity (exceeding 57 times its own weight) toward a variety of organic solvents and exhibited superior thermal insulating properties compared to the widely used sponge and cotton. This work demonstrates a versatile strategy for the synthesis and shaping of processable COF materials in water that will contribute to the development of COF monoliths for advanced applications.

Reprocessible Triketoenamine-Based Vitrimers with Closed-Loop Recyclability.

Development of thermosets that can be repeatedly recycled via both chemical route (closed-loop) and thermo-mechanical process is attractive and remains an imperative task. In this work, we reported a triketoenamine based dynamic covalent network derived from 2,4,6-triformylphloroglucinol and secondary amines. The resulting triketoenamine based network does not have intramolecular hydrogen bonds, thus reducing its π-electron delocalization, lowering the stability of the tautomer structure, and enabling its dynamic feature. By virtue of the highly reversible bond exchange, this novel dynamic covalent bond enables the easy construction of highly crosslinked and chemically reprocessable networks from commercially available monomers. The as-made polymer monoliths exhibit high mechanical properties (tensile strength of 79.4 MPa and Young's modulus of 571.4 MPa) and can undergo a monomer-network-monomer (yields up to 90 %) recycling mediated by an aqueous solution, with the new-generation polymer capable of restoring the material strength to its original state. In addition, owing to its dynamic nature, a catalyst-free and low-temperature reprogrammable covalent adaptable network (vitrimer) was achieved. The design concept reported herein can be applied to the development of other novel vitrimers with high repressibility and recyclability, and sheds light on future design of sustainable polymers with minimal environmental impact.

Interfacial Ti-S Bond Modulated S-Scheme MOF/Covalent Triazine Framework Nanosheet Heterojunctions for Photocatalytic C-H Functionalization.

Constructing photocatalyst systems to functionalize the inert C-H bonds has attracted extensive research interest. However, purposeful modulation of interfacial charge transfer in heterostructures remains a challenge, as it usually suffers from sluggish kinetics. Reported herein is an easy strategy to construct the heteroatom-induced interface for developing the titanium-organic frameworks (MOF-902) @ thiophene-based covalent triazine frameworks (CTF-Th) nanosheets S-scheme heterojunctions with controllable oxygen vacancies (OVs). Specifically, Ti atoms were first anchored onto the heteroatom site of CTF-Th nanosheets, and then grown into MOF-902 via an interfacial Ti-S linkage, generating OVs. Using in situ X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculations, the enhanced interfacial charge separation and transfer induced by moderate OVs in the pre-designed S-scheme nanosheets was validated. The heterostructures exhibited an improved efficiency in photocatalytic C3-acylation of indoles under mild conditions with a yield 8.2 times larger than pristine CTF-Th or MOF-902 and enabled an extended scope of substrates (15 examples). This performance is superior to state-of-the-art photocatalyst and can be retained, without significant loss, after 12 consecutive cycles.

A Vinylene-Bridged Conjugated Covalent Triazine Polymer as a Visible-Light-Active Photocatalyst for Degradation of Methylene Blue.

The development of new photocatalytic platforms using novel semiconductor material is an important challenge. Herein, a sp2 carbon-conjugated covalent triazine polymer (sp2 c-CTP-4), featuring a vinylene bridge and extended π-conjugation, is prepared as a highly efficient photocatalyst for degradation of methylene blue. sp2 c-CTP-4 exhibits substantial semiconducting properties such as enhanced charge transfer and prolonged lifetime of carriers compared to its counterparts with CN or CC connections, likely due to its extended π-delocalization with an unencumbered CC bridge. Moreover, benefiting from its high chemical stability, the as-made catalyst can be recycled five times with good retention of photocatalytic activity. This study provides a new pathway for constructing a robust platform for efficient photocatalysis and gives insight into the structure-property relationship of conjugated polymers.

Co(III)-Salen immobilized cellulose nanocrystals for efficient catalytic CO2 fixation into cyclic carbonates under mild conditions.

Searching for green, recyclable and highly efficient catalyst for the synthesis of cyclic carbonates from CO2 is of great importance because it is profitable for reducing the greenhouse effects and meets the principles of green chemistry. Herein, a series of cellulose nanocrystals, either the pristine or modified ones (TEMPO oxidized and Co(III)salen immobilized), were explored as catalysts for cycloaddition of epoxides and carbon dioxide. The impact of surface properties on the performance of the as-made catalysts was investigated. Co(III)-salen grafted cellulose nanocrystals was proven to be the most effective catalyst in this study, which could afford excellent yield up to 99 % after 24 h even under low CO2 pressures of 0.1 MPa. They can be easily recovered and reused for at least 4 times, demonstrating their excellent stability. We found that the surface functional groups such as enriched sulfate or carboxylic groups could also account for the enhanced catalytic activity. This work highlights the applications of green and sustainable nanoparticles in a cycloaddition reaction and offers a sustainable solution in industrial catalysis related to CO2 conversions.

Polarization-induced charge separation in conjugated microporous polymers for efficient visible light-driven C-3 selenocyanation of indoles.

Conjugated microporous polymers (CMPs) are cost-effective photocatalysts in organic transformations, while they are usually limited by the insufficient separation of photogenerated charges. Here we report a polarization strategy through molecular geometry optimization to promote the charge separation of CMPs. Three CMP photocatalysts with an alternative donor-acceptor skeleton and tunable symmetry were synthesized by the oxidative coupling of bis-carbazoles with electron-deficient bridges (benzene/pyridine/pyrimidine). Simply regulating the polarization of the starting monomers leads to tailorable porosity, photoelectric properties, and photocatalytic activity of the CMPs. They exhibited high efficiency in C-3 selenocyanation of indoles under visible-light and at room temperature, and pyridine-based CMPs with the largest dipole moment gave a yield of up to 94%, superior to their state-of-the-art photocatalyst counterparts. Photo-physical experiments combined with theoretical calculations further supported that the incorporation of the polarized linker introduced an internal electric field, benefitting efficient charge separation. This offered new insight into developing high-performance photocatalysts.

Facile preparation of CoO nanoparticles embedded N-doped porous carbon from conjugated microporous polymer for oxygen reduction reaction.

Developing cost-effective approaches for fabricating porous carbon (PC) based catalysts with favourable oxygen reduction reaction (ORR) performance is highly significant for fuel-cell devices. Herein, we reported a precursor controlled, molten salt-templated approach to prepare ultrafine CoO nanoparticles embedded nitrogen-doped PC materials with high surface area (1236 m2 g-1) and large pore volume (0.68 cm3 g-1). This method is simple and feasible, which produce CoO nanoparticles that were uniformly distributed on carbon skeleton with diameters in the range of 5-10 nm. The unexpected collapse of porous structures and agglomeration of metal nanoparticles were suppressed in the synthetic process. The as-made sample not only showed efficient catalytic activity towards ORR in alkaline media with a half wave potential (E1/2) of 0.85 V (vs. RHE), but also exhibited better stability and stronger resistance to methanol than Pt/C.