Millisecond Pulsed Films Unify the Mechanisms of Cellulose Fragmentation

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• 作者：Christoph Krumm ; Jim Pfaendtner ; Paul J. Dauenhauer
• 刊名：Chemistry of Materials
• 出版年：2016
• 出版时间：May 10, 2016
• 年：2016
• 卷：28
• 期：9
• 页码：3108-3114
• 全文大小：458K
• 年卷期：0
• ISSN：1520-5002

文摘

The mechanism of crystalline cellulose fragmentation has been debated between classical models proposing end-chain or intrachain scission to form short-chain (molten) anhydro-oligomer mixtures and volatile organic compounds. Models developed over the last few decades suggest global kinetics consistent with either mechanism, but validation of the chain-scission mechanism via measured reaction rates of cellulose has remained elusive. To resolve these differences, we introduce a new thermal-pulsing reactor four orders of magnitude faster than conventional thermogravimetic analysis (10⁶ vs 10² °C/min) to measure the millisecond-resolved evolution of cellulose and its volatile products at 400–550 °C. By comparison of cellulose conversion and furan product formation kinetics, both mechanisms are shown to occur with the transition from chain-end scission to intrachain scission above 467 °C concurrent with liquid formation comprised of short-chain cellulose fragments.