Colloidal three-dimensional covalent organic frameworks and their application as porous liquids

Mow, Rachel E.; Lipton, Andrew S.; Shulda, Sarah; Gaulding, E. Ashley; Gennett, Thomas; Braunecker, Wade A.

doi:10.1039/d0ta06768g

Cited by 45 publications

(48 citation statements)

References 55 publications

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“…The FTIR spectra of TpDPP nano-spheres displayed intense peaks at 1600-1625 (-C=O), 1579 (-C=C), 1277 cm -1 (-C-N), and peaks at 1671 (-C=O of free -CHO), 2851-2920 (-C-H of free -CHO), 3067-3352 cm -1 (-N-H stretching of free -NH 2 ) (Figure S5). The FTIR spectra suggested the formation of a βketoenamine backbone [30][31][32] and the presence of free aldehyde and amine functionalities on the sphere surface. The presence of free aldehyde and amine functionalities indicates incomplete crystallization and structural defects.…”

Section: Resultsmentioning

confidence: 99%

Heterogeneous C–H Functionalization in Water via Porous Covalent Organic Framework Nanofilms: A Case of Catalytic Sphere Transmutation

et al. 2021

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Heterogeneous catalysis in water has not been explored beyond certain advantages like recyclability and recovery of the catalysts from the reaction medium. In doing so, they often fail to address other authentic pitfalls of homogeneous catalysis. Moreover, poor yield, extremely low selectivity, and active catalytic sites' deactivation further underrate the heterogeneous catalysis in water. On the other hand, most of the synthetically useful homogeneous catalysts are either water intolerant or remain catalytically inactive in water. Considering these facts, we have rationally designed and synthesized solution dispersible porous covalent organic framework (COF) nano-spheres to utilize their distinctive morphology and dispersibility to bridge between homogeneous and heterogeneous catalysis. The success has further been extended in fabricating catalyst immobilized COF thin-lms via covalent self-assembly for the very rst time. We have used these catalyst immobilized COF thin-lms to develop a general methodology for the C-H functionalization of organic substrates in water. This unique covalent self-assembly occurs through the protrusion of the bers/threads at the interface of two nano-spheres, transmuting the catalytic spheres into lms without any leaching of catalyst molecules, which was hitherto unheard of. The catalyst immobilized porous COF thin-lms' chemical functionality and hydrophobic environment stabilizes the high valent transient active oxoiron(V) intermediate in water and restricts the active catalytic site's deactivation. An elevated catalytic yield and high selectivity (3°:2°) have been achieved in open-air conditions at room temperature, accompanying the elemental feature of heterogeneous catalysis, i.e., the recyclability. These COF lms functionalized the unactivated C-H bonds in water with a high catalytic yield (45-99%) and with a high degree of selectivity (cis:trans=155:1; 3°:2°=257:1 in case of cis-1,2dimethylcyclohexane). To establish the "practical implementation" of this approach, we conducted the in ow catalysis (Turnover Number = 355±5) using catalyst immobilized COF lms fabricated on a macroporous polymeric support.

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Section: Resultsmentioning

confidence: 99%

Heterogeneous C–H Functionalization in Water via Porous Covalent Organic Framework Nanofilms: A Case of Catalytic Sphere Transmutation

et al. 2021

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“…in hindered solvents (e.g., 15‐crown‐5, 18‐crown‐6, poly(dimethylsiloxane), phosphonium‐based ionic liquid and branched ionic liquids. ); [ 2,5–14 ] suitable surface engineering of porous structures (e.g., hollow silica and silicalite‐1 with an organosilane, as well as hollow carbon spheres with polymerized ionic liquids as coronas, respectively, which were subsequently modified with an ionic attachment of liquid polyethylene glycol chains as canopy; [ 3,15–17 ] ) as well as the liquefaction of metal–organic framework (i.e., ZIF‐4) above its melting temperature. [ 18 ] However, preparing liquid porous materials with permanent porosity is still challenging due to several obstacles, such as the intermolecular self‐filling phenomenon, easy collapse and decomposition of the discrete hosts, as well as the setting and agglomeration of the microporous structures, and more.…”

Section: Methodsmentioning

confidence: 99%

An In Situ Coupling Strategy toward Porous Carbon Liquid with Permanent Porosity

Wang

Zhang

et al. 2021

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An in situ coupling approach is used to fabricate the porous carbon liquid with permanent porosity by directly dispersing hollow carbon nanospheres in polymerized ionic liquids. It is a kind of homogenous and stable type III porous liquid at room temperature. Because of the well‐preserved permanent porosity, this unique porous carbon liquid is capable of absorbing the largest quantity of carbon dioxide than the reference PILs and solid carbon liquid, thus, can function as a promising candidate for application in gas storage. More importantly, this approach not only provides an easy method to tune the properties of those specific porous liquids, but also is suitable for fabricating other porous liquid based on varied porous structures (e.g., porous carbon nitride, porous boron nitride, and polymer with intrinsic microporosity), thus paving a viable path for the rational design and synthesis of novel porous liquids with functional properties for specific applications.

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“…Further, meso‐ and microporous liquids have also been designed by surface engineering MOFs with oligomer species or polyethylene glycol, and also by the dissolution of MOFs in other solvents such as crown ethers and poly(dimethylsiloxane) [44–47] . Highly stable 3D‐imine‐linked colloidal covalent organic framework (COF) based porous liquid have been developed with increased CO 2 and CH 4 uptake capacity [48] . Various methods and techniques have been utilized to develop porous polymeric, MOF or COF based porous ionic liquids for various applications such as adsorption of phenolic compounds, [49] CO 2 capture, [50,51] extractive desulphurization of fuels, [52] separation of 2,2,3,3‐tetrafluoro‐1‐propanol from aqueous solution, [53] catalyst for C−C coupling reaction [54] .…”

Section: Introductionmentioning

confidence: 99%

Composite Porous Liquid for Recyclable Sequestration, Storage and In Situ Catalytic Conversion of Carbon Dioxide at Room Temperature

2021

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Permanent pores combined with fluidity renders flow processability to porous liquids otherwise not seen in porous solids. Although porous liquids have been utilized for sequestration of different gases and their separation, there is still a dearth of studies for deploying in situ chemical reactions to convert adsorbed gases into utility chemicals. Here, we show the design and development of a new type of solvent‐less and hybrid (meso‐)porous liquid composite, which, as demonstrated for the first time, can be used for in situ carbon mineralization of adsorbed CO2. The recyclable porous liquid composite comprising polymer‐surfactant modified hollow silica nanorods and carbonic anhydrase enzyme not only sequesters (5.5 cm3 g−1 at 273 K and 1 atm) and stores CO2 but is also capable of driving an in situ enzymatic reaction for hydration of CO2 to HCO3− ion, subsequently converting it to CaCO3 due to reaction with pre‐dissolved Ca2+. Light and electron microscopy combined with X‐ray diffraction reveals the nucleation and growth of calcite and aragonite crystals. Moreover, the liquid‐like property of the porous composite material can be harnessed by executing the same reaction via diffusion of complimentary Ca2+ and HCO3− ions through different compartments separated by an interfacial channel. These studies provide a proof of concept of deploying chemical reactions within porous liquids for developing utility chemical from adsorbed molecules.

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Colloidal three-dimensional covalent organic frameworks and their application as porous liquids

Abstract: Colloidal COFs suspended in a bulky, size-excluded ionic liquid create a ‘porous liquid’ with enhanced gas uptake.

Cited by 45 publications

References 55 publications

Heterogeneous C–H Functionalization in Water via Porous Covalent Organic Framework Nanofilms: A Case of Catalytic Sphere Transmutation

Heterogeneous C–H Functionalization in Water via Porous Covalent Organic Framework Nanofilms: A Case of Catalytic Sphere Transmutation

An In Situ Coupling Strategy toward Porous Carbon Liquid with Permanent Porosity

Composite Porous Liquid for Recyclable Sequestration, Storage and In Situ Catalytic Conversion of Carbon Dioxide at Room Temperature

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