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Engineering Porous Organic Cage Crystals with Increased Acid Gas Resistance
Authors:Guanghui Zhu  Christopher D. Hoffman  Yang Liu  Souryadeep Bhattacharyya  Dr. Uma Tumuluri  Melinda L. Jue  Dr. Zili Wu  Dr. David S. Sholl  Dr. Sankar Nair  Dr. Christopher W. Jones  Dr. Ryan P. Lively
Affiliation:1. School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA;2. Chemical Sciences Division and Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA
Abstract: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.
Keywords:acid gas interactions  cage compounds  grain boundaries  microporous materials  sulfur dioxide
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