A spectrokinetic methodology was developed to determine reactive surface species by combining operando ultraviolet–visible spectroscopy and charge transfer kinetic models. The methodology consisted of three general steps: 1) concomitant measurement of reaction rates and charge transfer via ultraviolet–visible spectroscopy; 2) development of rate expressions from kinetic models involving the adsorbed species of interest. These rate expressions relate reaction rates, charge transfer, and partial pressures of gas phase species; and 3) evaluation of the goodness of fit of the rate expressions to the experimental data. The species whose rate expressions show the best fit are the more likely reactive surface species for the studied reaction. An example is presented for the determination of reactive oxygen species during ethanol oxidation over Au/TiO. The charge transfer spectrokinetic analysis showed that surface hydroperoxyl, hydroxyl, and atomic oxygen species were reactive surface intermediates, whereas surface molecular oxygen was not.

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研究活性表面物种的通用方法，CT-SKAn：电荷转移光谱动力学分析


开发了一种光谱动力学方法，通过结合操作紫外-可见光谱和电荷转移动力学模型来确定活性表面物种。该方法由三个一般步骤组成：1）通过紫外-可见光谱同时测量反应速率和电荷转移； 2) 根据涉及感兴趣的吸附物质的动力学模型开发速率表达式。这些速率表达式与反应速率、电荷转移和气相物质的分压有关； 3）评估速率表达式与实验数据的拟合优度。速率表达式显示最佳拟合的物种是所研究反应更可能的反应性表面物种。给出了在 Au/TiO 上乙醇氧化过程中测定活性氧的示例。电荷转移光谱动力学分析表明，表面氢过氧基、羟基和原子氧物种是反应性表面中间体，而表面分子氧则不是。