4.6 Article

Engineering Porous Organic Cage Crystals with Increased Acid Gas Resistance

期刊

CHEMISTRY-A EUROPEAN JOURNAL
卷 22, 期 31, 页码 10743-10747

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201601659

关键词

acid gas interactions; cage compounds; grain boundaries; microporous materials; sulfur dioxide

资金

  1. UNCAGE-ME, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012577]

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Both known and new CC3-based porous organic cages are prepared and exposed to acidic SO2 in vapor and liquid conditions. Distinct differences in the stability of the CC3 cages exist depending on the chirality of the diamine linkers used. The acid catalyzed CC3 degradation mechanism is probed via in situ IR and a degradation pathway is proposed and supported with computational results. CC3 crystals synthesized with racemic mixtures of diaminocyclohexane exhibited enhanced stability compared to CC3-R and CC3-S. Confocal fluorescent microscope images reveal that the stability difference in CC3 species originates from an abundance of mesoporous grain boundaries in CC3-R and CC3-S, allowing facile access of aqueous SO2 throughout the crystal, promoting decomposition. These grain boundaries are absent from CC3 crystals made with racemic linkers.

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