Abstract Despite recent advances, little has been experimentally established regarding the detailed chemical processes that occur during biomass pyrolysis reactions. We developed a new technique that allows for the monitoring of each molecular product from fast pyrolysis with ∼0.2 s temporal resolution. This was achieved by directly coupling a micropyrolyzer with a time-of-flight mass spectrometer via a soft ionization. Molecular products studied were produced in thin-film pyrolysis of a series of glucose-based carbohydrates. Unprecedented details of the pyrolysis reaction process were revealed, including the timescale of molecular product formation and the existence of metastable intermediates. Small carbohydrates are completely pyrolyzed within one second and as short as one-half second for glucose pyrolysis. Individual time profiles could be extracted and examined for each molecular product. Additionally, the effect of sample dimensions on the pyrolysis of cellulose and α-cyclodextrin, as both thin films and particles, was studied. A surprising time delay of one second is observed for the thin-film pyrolysis of cellulose and α-cyclodextrin, which is attributed to the transition to the molten phase. When a large amount of cellulose or α-cyclodextrin is pyrolyzed, random fluctuations of temporal profiles are observed and explained as coming from aerosol ejections. This is well correlated with the high abundance of non-volatile products such as cellobiosan that cannot be detected in typical GC–MS or pyrolysis GC–MS analysis.

中文翻译：

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用于以亚秒时间分辨率跟踪碳水化合物快速热解中分子产物的新型仪器

摘要 尽管最近取得了进展，但关于生物质热解反应过程中发生的详细化学过程的实验还很少。我们开发了一种新技术，可以监测来自快速热解的每个分子产物，时间分辨率约为 0.2 秒。这是通过软电离直接将微热解器与飞行时间质谱仪耦合来实现的。所研究的分子产品是在一系列基于葡萄糖的碳水化合物的薄膜热解中生产的。揭示了热解反应过程的前所未有的细节，包括分子产物形成的时间尺度和亚稳态中间体的存在。小碳水化合物在一秒内完全热解，葡萄糖热解只需二分之一秒。可以为每个分子产物提取和检查单独的时间曲线。此外，还研究了样品尺寸对作为薄膜和颗粒的纤维素和 α-环糊精热解的影响。对于纤维素和α-环糊精的薄膜热解，观察到令人惊讶的一秒的时间延迟，这归因于向熔融相的转变。当大量纤维素或 α-环糊精被热解时，会观察到时间分布的随机波动，并将其解释为来自气溶胶喷射。这与在典型 GC-MS 或热解 GC-MS 分析中无法检测到的高丰度非挥发性产品（如纤维二糖）密切相关。研究了样品尺寸对作为薄膜和颗粒的纤维素和 α-环糊精热解的影响。对于纤维素和α-环糊精的薄膜热解，观察到令人惊讶的一秒的时间延迟，这归因于向熔融相的转变。当大量纤维素或 α-环糊精被热解时，会观察到时间分布的随机波动，并将其解释为来自气溶胶喷射。这与在典型 GC-MS 或热解 GC-MS 分析中无法检测到的高丰度非挥发性产品（如纤维二糖）密切相关。研究了样品尺寸对作为薄膜和颗粒的纤维素和 α-环糊精热解的影响。对于纤维素和α-环糊精的薄膜热解，观察到令人惊讶的一秒的时间延迟，这归因于向熔融相的转变。当大量纤维素或 α-环糊精被热解时，会观察到时间分布的随机波动，并将其解释为来自气溶胶喷射。这与在典型 GC-MS 或热解 GC-MS 分析中无法检测到的高丰度非挥发性产品（如纤维二糖）密切相关。当大量纤维素或 α-环糊精被热解时，会观察到时间分布的随机波动，并将其解释为来自气溶胶喷射。这与在典型 GC-MS 或热解 GC-MS 分析中无法检测到的高丰度非挥发性产品（如纤维二糖）密切相关。当大量纤维素或 α-环糊精被热解时，会观察到时间分布的随机波动，并将其解释为来自气溶胶喷射。这与在典型 GC-MS 或热解 GC-MS 分析中无法检测到的高丰度非挥发性产品（如纤维二糖）密切相关。