Wu Dongxiang, Zhu Yaguang, Shan Weitao, Wang Jianyu, Liu Qianqian, Zhou Guangwen
Department of Mechanical Engineering & Materials Science and Engineering Program, State University of New York, Binghamton, New York 13902, United States.
J Phys Chem Lett. 2022 Mar 17;13(10):2396-2403. doi: 10.1021/acs.jpclett.1c04145. Epub 2022 Mar 8.
Identifying the atomic structure and formation mechanism of intermediates during chemical transformations is challenging because of their short-lived nature. With a combination of microscopic and spectroscopic measurements and first-principles calculations, herein we report the formation of a metastable intermediate Cu-O/OH superstructure during the reaction of hydrogen with oxygen-covered Cu(110). This superstructure resembles the parent (6 × 2)-O phase and can be termed as (6 × 2)-(4O+2OH) with OH groups occupying the missing Cu sites between isolated Cu atoms. Using atomistic calculations, we elucidate the reaction pathways leading to the (6 × 2)-(4O+2OH) formation via both molecular and dissociative H adsorption. These results demonstrate the complex surface dynamics resulting from the parallel reaction pathways and may open up the possibility of directing the reaction dynamics by deliberately manipulating transient surface structure and composition.
由于中间体的寿命短暂，确定化学转化过程中中间体的原子结构和形成机制具有挑战性。通过结合微观和光谱测量以及第一性原理计算，我们在此报告了氢气与氧覆盖的Cu(110)反应过程中形成了一种亚稳中间体Cu-O/OH超结构。这种超结构类似于母体(6×2)-O相，可称为(6×2)-(4O+2OH)，其中OH基团占据孤立铜原子之间缺失的铜位点。通过原子计算，我们阐明了通过分子氢吸附和解离氢吸附导致(6×2)-(4O+2OH)形成的反应途径。这些结果证明了平行反应途径导致的复杂表面动力学，并可能通过有意操纵瞬态表面结构和组成来指导反应动力学。
