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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Time-Resolved Study of Acetyl Radical in Zeolite NaY by Step-Scan FT-IR Spectroscopy
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Time-Resolved Study of Acetyl Radical in Zeolite NaY by Step-Scan FT-IR Spectroscopy

机译：逐步扫描FT-IR光谱法对NaY沸石中乙酰基的时间分辨研究

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摘要

Step-scan FT-infrared spectroscopy of 1-naphthyl acetate and pinacolone photodissociation in zeolite NaY revealed a transient at 2125 cm~(-1) assigned to acetyl radical. Comparison of the intensities of transient and final product absorptions, 2-acetyl-1-naphthol in the case of naphthyl acetate and acetaldehyde for pinacolone, indicates that the acetyl radical represents the main, and probably only, reaction channel. The decay of the radical at room temperature is best described by a single-exponential law with a lifetime of 71 ± 15 μs (1-naphthyl acetate) and 315 ± 30 μs (pinacolone). This constitutes the first detection and kinetic study of a small transient radical in a zeolite. The kinetic result is interpreted in terms of complete separation of the photogenerated pairs from the parent supercage, followed by random walks in subspaces of the zeolite lattice imposed by the much less mobile precursor molecules. These force the geminate radicals to react and thereby contribute to the high selectivity of these photoreactions.
机译：乙酸1-萘酯和频哪酮光解离在NaY沸石中的步进扫描FT红外光谱显示在2125 cm〜（-1）处有一个乙酰基自由基存在。比较醋酸萘萘酯的乙酸萘酯和乙醛中的2-乙酰基-1-萘酚的瞬态和最终产物的吸收强度，表明乙酰基代表了主要的反应通道，可能只是唯一的反应通道。自由基在室温下的衰变最好用单指数定律描述，其寿命为71±15μs（乙酸1-萘酯）和315±30μs（频哪酮）。这是对沸石中一个小的瞬态自由基的首次检测和动力学研究。动力学结果的解释是将光生对完全从母体超笼中分离出来，然后在流动性差得多的前体分子施加的沸石晶格的子空间中随机游走。这些迫使基自由基反应，从而有助于这些光反应的高选择性。

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