Transient spectroscopic surface-chemistry experiments in combination with spatially resolved kinetic Monte Carlo (KMC) simulations offer great potential to gain a wealth of molecular information on the kinetics of catalytic surface reactions as exemplified by the CO oxidation reaction over RuO₂(110). This approach surpasses the common problem that in the steady-state reactions, the prevailing species detectable by in operando surface-sensitive spectroscopy are frequently spectator species, thereby obscuring the reactive surface species. Our experiment is sensitive to the relative activity of different oxygen species by saturating the surface with loosely bound oxygen, leaving only single vacancies where CO can adsorb and recombine with oxygen. With in situ reflection–absorption infrared spectroscopy (RAIRS) in combination with ab initio based KMC simulations, we follow the time evolution toward steady state (transient experiment). In this way, we are able to resolve a long-standing controversy about the active oxygen species in the CO oxidation over RuO₂(110), evidencing that both surface O species (O_br and O_ot) are equally active, although their adsorption energies differ by more than 150 kJ/mol.

中文翻译：

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结合瞬态吸收-吸收红外光谱和动力学蒙特卡洛模拟，探索RuO ₂（110）上CO氧化过程中不同氧的活度

瞬态光谱表面化学实验与空间分辨动力学蒙特卡洛（KMC）模拟相结合提供了巨大的潜力，可获取有关催化表面反应动力学的大量分子信息，例如RuO _2上的CO氧化反应（110）。这种方法克服了一个普遍的问题，即在稳态反应中，可通过操作表面敏感光谱法检测到的主要物质通常是旁观者，从而掩盖了反应性表面物质。我们的实验通过用松散结合的氧饱和表面，从而对不同氧种类的相对活性敏感，仅留下一个空位，CO可以吸收氧并与氧重新结合。结合原位反射吸收红外光谱（RAIRS）和基于从头算的KMC模拟，我们跟踪了时间向稳态发展的过程（瞬态实验）。这样，我们就可以解决关于RuO _2上的CO氧化中的活性氧种类的长期争议。（110），证明两个表面O物种（O _br和O _ot）都具有相同的活性，尽管它们的吸附能相差150 kJ / mol以上。