Large Calixarenes

Talotta, Carmen; Gaeta, Carmine; Soriente, Annunziata; Rosa, Margherita De; Geraci, Corrada; Neri, Placido

doi:10.1007/978-3-319-31867-7_7

Cited by 2 publications

(1 citation statement)

References 85 publications

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“…This was because the structural flexibility of SCA molecules, which originated from the flexible methylene linker between their constituting monomers, increased with size. [34] As such, larger SCA molecules could better adapt to the compressive or tensile forces during mechanical strain. More specifically, STCA4 molecules with the least number of monomers and smallest cavity size possessed more conformational rigidity than SCA6 and SCA8 because their bottom rim hydroxyl groups were within closer proximity with each other to engage in mutual hydrogen bonding that upheld the bowl-shape conformation.…”

Section: Resultsmentioning

confidence: 99%

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO₂ Capture

Liang

Naderi

et al. 2021

Advanced Materials

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Processable molecular‐sieving membranes are important materials for realizing energy‐efficient precombustion CO2 capture during industrial‐scale hydrogen production. However, the promising design of mixed matrix membranes (MMMs) that aims to integrate the molecular‐sieving properties of nanoporous architectures with industrial processable polymers still faces performance and fabrication issues due to the formation of segregated nanofiller domains in their polymer matrices. Here, an unconventional nanocomposite membrane design is proposed using soluble organic macrocyclic cavitands (OMCs) with tunable open cavity sizes that not only mitigate the formation the discrete nanofiller phases but also deliver distinct molecular‐sieving separations. The versatile organic‐solvent solubility coupled with highly interactive functionalities of OMCs allows them to obtain molecularly homogeneous mixing with matrix polymers and form only one integral continuous phase crucial to the robust processability of polymers. A series of polybenzimidazole‐based molecularly mixed composite membranes (MMCMs) are fabricated via the incorporation of a soluble and thermally stable OMC choice, sulfocalixarenes, with various cavity sizes. These membranes achieve outstanding high‐temperature mixed‐gas H2/CO2 separation performances comparable with several state‐of‐the‐art molecular‐sieving membranes owing to effective size‐sieving gas passages through the open or partially‐intruded supramolecular cavities. The broadly tunable structures and functionalities of OMCs would make their MMCMs attractive for other energy‐intensive molecular separations.

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Section: Resultsmentioning

confidence: 99%

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO₂ Capture

Liang

Naderi

et al. 2021

Advanced Materials

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Supramolecular Polymer Network Membranes with Molecular‐Sieving Nanocavities for Efficient Pre‐Combustion CO₂ Capture

Chung

2021

Small Methods

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Pre‐combustion membrane CO2 capture from syngas before utilizing the clean hydrogen fuel, demands very challenging membrane materials with simultaneous high thermal resistance, precise subnanometer size‐selectivity, and robust processability. Here, an unconventional yet ultra‐facile nanocomposite membrane design using 4‐sulfocalix[4]arene (SCA4) molecules, a highly interactive member of soluble organic macrocyclic cavitands (OMCs) with a precise ≈3.0Å open cavity, is reported, to effectively sieve CO2 (3.3Å) from H2 (2.89Å). By simply infiltrating dissolved SCA4 molecules into prefabricated polymer membranes, they form extensive 3D supramolecular polymer networks (SPNs) with the polymer backbones through multi‐site ionic interactions. Bearing distinctly molecular‐sieving nanocavities, these otherwise amorphous SPN membranes deliver drastically enhanced mixed‐gas H2/CO2 separation under an industrial high‐temperature‐and‐pressure environment with 4.35 times higher selectivity being achieved, allowing them to well outperform most existing polymer‐based materials and even rival many state‐of‐the‐art but delicate inorganic and framework‐based membranes. They also demonstrate enhanced mechanical properties and long‐term operation stability. Most attractively, the SPN membranes obtain a molecularly homogeneous, single‐phase composite structure that can significantly surpass conventional phase‐segregated mixed‐matrix membranes in processability. Accompanied by the widely tunable OMC structures, this work can provide a versatile toolbox for designing advanced molecular‐sieving membranes with an optimal balance of performance, robust properties, and scalability.

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Large Calixarenes

Cited by 2 publications

References 85 publications

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO₂ Capture

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO₂ Capture

Supramolecular Polymer Network Membranes with Molecular‐Sieving Nanocavities for Efficient Pre‐Combustion CO₂ Capture

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Large Calixarenes

Cited by 2 publications

References 85 publications

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO2 Capture

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO2 Capture

Supramolecular Polymer Network Membranes with Molecular‐Sieving Nanocavities for Efficient Pre‐Combustion CO2 Capture

Contact Info

Product

Resources

About

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO₂ Capture

Tunable Supramolecular Cavities Molecularly Homogenized in Polymer Membranes for Ultraefficient Precombustion CO₂ Capture

Supramolecular Polymer Network Membranes with Molecular‐Sieving Nanocavities for Efficient Pre‐Combustion CO₂ Capture