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Probing Regional Hydrophobicity of Zeolite-Confined Cyclopentenyl Cations under Humid Conditions by Solid-State NMR
Jue Kang1,2, Chao Wang1, Min Hu1
1National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance Spectroscopy and Imaging, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China.
Abstract:
Cyclopentenyl cations, crucial intermediates in zeolite-catalyzed hydrocarbon transformations, exhibit unique dual hydrophobicity-hydrophilicity due to their polar cationic centers and nonpolar alkyl groups. This study investigates their regional hydrophobicity under moist environments using multidimensional solid-state NMR spectroscopy with propane as a probe molecule. We demonstrate that water enhances noncovalent interactions between cyclopentenyl cations and propane in ZSM-5 channels, primarily through the alkyl groups, confirming their regional hydrophobic character. Competitive adsorption experiments using dichloromethane (dielectric constant, ε = 8.9) further highlight the critical role of solvent polarity (εwater = 80.1) in promoting hydrophobic interactions. A surfactant-like assembly mechanism is proposed, where water repels propane from Brønsted acid sites in zeolite, driving its accumulation near hydrophobic alkyl regions.
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