在高温下对Pd(332) 进行催化氨氧化过程的机制和速率决定步骤
Jan Fingerhut1, Jessalyn A DeVine2, Rongrong Yin3
1Institute for Physical Chemistry, University of Göttingen, 37077 Göttingen, Germany.
概括
这项研究揭示了在催化剂上氧化氨的速度决定性步骤是N* + O* → N*O反应. 这一发现澄清了工业酸生产中副产品的形成.
科学领域:
- 表面科学是一门科学.
- 化学动力学 化学动力学
- 催化剂是一种催化剂.
背景情况:
- 组金属上的氨氧化对于酸生产至关重要.
- 准确的反应机制仍然不完全理解和辩论.
- 催化剂在工业应用中被广泛使用.
研究的目的:
- 在模型Pd(332) 催化剂上阐明氨氧化的详细机制.
- 为了确定速度决定的步骤和关键反应中间体.
- 解释观察到的副产品的形成.
主要方法:
- 速度解析的动力学测量.
- 对于中间检测的五秒激光诱导脱吸 (N*).
- 密度函数理论和过渡状态理论计算.
主要成果:
- 水 (H2O) 迅速形成,而氧化 (NO) 的形成则延迟.
- 反应中间体N*是最长寿的物种.
- 在步骤位点的N* + O* → N*O反应被确定为速度决定的步骤.
- N*O 脱吸是通过共同吸收的氧气加速的.
结论:
- 提出了一种全面的机制来解释Pd{332}上的氨氧化.
- 识别的速率决定步骤提供了对副产品 (N2,N2O) 形成的洞察力.
- 了解这些机制可以优化工业酸合成.
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