Bispropylurea bridged polysilsesquioxane: A microporous MOF-like material for molecular recognition

TL;DR

This study introduces bispropylurea bridged POSS, a microporous material with MOF-like properties, demonstrating high selectivity and capacity for acetonitrile adsorption, useful for VOC applications.

Contribution

The paper reports the synthesis, structural characterization, and molecular recognition capabilities of a novel POSS-based material with high selectivity for acetonitrile.

Findings

POSS-urea exhibits an adsorption level of 74 mmol/g for acetonitrile.

The material's acetonitrile adsorption capacity is 132 times higher than for toluene.

Structural analysis shows pores around 1 nm with irregular placement.

Abstract

Microporous organosilicas assembled from polysilsesquioxane (POSS) building blocks are promising materials that are yet to be explored in-depth. Here, we investigate the processing and molecular structure of bispropylurea bridged POSS (POSS-urea), synthesised through the acidic condensation of 1,3-bis(3-(triethoxysilyl)propyl)urea (BTPU). Experimentally, we show that POSS-urea has excellent functionality for molecular recognition toward acetonitrile with an adsorption level of 74 mmol/g, which compares favourably to MOFs and zeolites, with applications in volatile organic compounds (VOC). The acetonitrile adsorption capacity was 132-fold higher relative to adsorption capacity for toluene, which shows the pores are highly selective towards acetonitrile adsorption due to their size and arrangement. Theoretically, our tight-binding density functional and molecular dynamics calculations demonstrated that this BTPU based POSS is microporous with an irregular placement of the pores. Structural studies confirm maximal pore sizes of around 1 nm, with POSS cages possessing an approximate edge length of approximately 3.16 Angstrom