Francesco Tavani, Federico Frateloreto, Daniele Del Giudice, Giorgio Capocasa, Marika Di Berto Mancini, Matteo Busato, Osvaldo Lanzalunga*, Stefano Di Stefano* and Paola D’Angelo*,
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引用次数: 0
Abstract
Oscillating reactions are among the most intriguing phenomena in chemistry, but many questions on their mechanisms still remain unanswered, due to their intrinsic complexity and to the low sensitivity of the most common spectroscopic techniques toward the reaction brominated species. In this work, we investigate the cerium ion-catalyzed Belousov–Zhabotinsky (BZ) oscillating reaction by means of time-resolved X-ray absorption spectroscopy (XAS), in combination with UV-vis spectroscopy and unsupervised machine learning, multivariate curve resolution, and kinetic analyses. Altogether, we provide new insights into the collective oscillatory behavior of the key brominated species involved in the classical BZ reaction and measure previously unreported oscillations in their concentrations through Br K-edge XAS, while simultaneously tracking the oscillatory Ce4+-to-Ce3+ transformation by coupling XAS with UV-vis spectroscopy. Our work evidences the potential of the XAS technique to investigate the mechanisms of oscillatory chemical systems whose species are often not detectable with conventional experimental methods.
振荡反应是化学中最引人入胜的现象之一,但由于其内在的复杂性以及最常见的光谱技术对反应溴化物的灵敏度较低,有关其机理的许多问题仍未得到解答。在这项工作中,我们通过时间分辨 X 射线吸收光谱(XAS),结合紫外可见光谱和无监督机器学习、多元曲线解析和动力学分析,研究了铈离子催化的别洛索夫-扎博金斯基(BZ)振荡反应。总之,我们对参与经典 BZ 反应的关键溴化物种的集体振荡行为提出了新的见解,并通过 Br K-edge XAS 测量了以前未报道过的它们的浓度振荡,同时通过 XAS 与紫外可见光谱的耦合跟踪了 Ce4+ 到 Ce3+ 的振荡转化。我们的工作证明了 XAS 技术在研究振荡化学系统机制方面的潜力,这些系统中的物种通常无法用传统实验方法检测到。
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.