Hydrogen Storage in Microporous Hypercrosslinked Organic Polymer Networks

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• 作者：Colin D. Wood ; Bien Tan ; Abbie Trewin ; Hongjun Niu ; Darren Bradshaw ; Matthew J. Rosseinsky ; Yaroslav Z. Khimyak ; Neil L. Campbell ; Ralph Kirk ; Ev Stö ; ckel ; Andrew I. Cooper
• 刊名：Chemistry of Materials
• 出版年：2007
• 出版时间：April 17, 2007
• 年：2007
• 卷：19
• 期：8
• 页码：2034 - 2048
• 全文大小：571K
• 年卷期：v.19,no.8(April 17, 2007)
• ISSN：1520-5002

文摘

A series of hypercrosslinked polymer networks has been synthesized by the self-condensation ofbischloromethyl monomers such as dichloroxylene (DCX), 4,4'-bis(chloromethyl)-1,1'-biphenyl (BCMBP),and 9,10-bis(chloromethyl)anthracene (BCMA). These materials are predominantly microporous and exhibitBrunauer-Emmett-Teller (BET) surface areas of up to 1904 m²/g as measured by N₂ adsorption at 77.3K (Langmuir surface area = 2992 m²/g). Networks based on BCMBP exhibit a gravimetric storage capacityof 3.68 wt % at 15 bar and 77.3 K, the highest yet reported for an organic polymer. The micro- andmesostructure of the networks is explained by a combination of solid-state NMR, gas sorptionmeasurements, pycnometry, and molecular simulations. The isosteric heat of sorption for H₂ on thesematerials is found to be in the range 6-7.5 kJ/mol. A molecular model is presented for a p-DCX networkthat simulates well certain key physical properties such as pore volume, pore width, absolute density,and bulk density. This model also predicts the isotherm shape and isosteric heat for H₂ sorption at 77.3and 87.2 K but overestimates the absolute degree of H₂ uptake, most likely because of a degree of occluded,inaccessible porosity in the real physical samples.