Wang Jianyu, Patel Shyam, Boscoboinik Jorge Anibal, Hunt Adrian, Waluyo Iradwikanari, Zhou Guangwen
Department of Mechanical Engineering & Materials Science and Engineering Program, State University of New York at Binghamton, Binghamton, New York 13902, United States.
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States.
J Phys Chem Lett. 2024 Oct 17;15(41):10375-10383. doi: 10.1021/acs.jpclett.4c02218. Epub 2024 Oct 7.
This study investigates the oxidation behavior of CuPt(100) in CO using a combination of ambient-pressure X-ray photoelectron spectroscopy, mass spectroscopy, and density functional theory modeling. Our in situ measurements reveal the simultaneous oxidation and reduction of CuO due to the opposing effects of atomic oxygen and CO generated from dissociative CO adsorption, leading to a dynamic equilibrium state of simultaneously occurring redox reactions. Complementary atomistic calculations elucidate the inhibitory effects of subsurface Pt enrichment and the counteracting roles of CO and CO in surface oxidation and reduction. These results provide mechanistic insights into the dissociative pathway of CO molecules and dynamic evolution of surface composition and reactivity of Cu-based alloy catalysts in CO-rich environments, with broader implications for tuning gas-surface reactions by manipulating gas reactants or solid surface composition.
本研究结合常压X射线光电子能谱、质谱和密度泛函理论建模，探究了CuPt(100)在CO中的氧化行为。我们的原位测量揭示，由于解离吸附的CO产生的原子氧和CO的相反作用，导致CuO同时发生氧化和还原，从而形成氧化还原反应同时发生的动态平衡态。互补的原子计算阐明了表面下Pt富集的抑制作用以及CO和CO在表面氧化和还原中的抵消作用。这些结果为CO分子的解离途径以及富CO环境中Cu基合金催化剂的表面组成和反应性的动态演变提供了机理见解，对于通过操纵气体反应物或固体表面组成来调节气-固表面反应具有更广泛的意义。
