揭示超小铂团簇中原子的不平等性:氧吸附仅限于原子最上层

Federico Loi, Luca Bignardi, Deborah Perco, Andrea Berti, Paolo Lacovig, Silvano Lizzit, Aras Kartouzian, Ulrich Heiz, Dario Alfè, Alessandro Baraldi
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引用次数: 0

摘要

原子和分子优先吸附位点的概念在异相催化中具有重要意义。对于超小尺寸的选择性团簇,由于其尺寸减小、结构特殊,区分每个原子在反应中的作用极具挑战性。本文揭示了组成石墨烯支持的 Pt12 和 Pt13 团簇的不等价原子在光诱导解离 O2 的过程中的不同表现,其中只有团簇最上层的原子参与了反应。在这一过程中,外延石墨烯支撑起着根本性的积极作用:簇群的存在所诱导的石墨烯波纹和针刺对于确定铂原子团聚体上的优先吸附位点至关重要,促进了物理吸附氧的横向扩散距离,从而诱导其选择性地吸附在簇群的最上层,并诱导簇群内部的不均匀电荷分布,这直接影响了对 O2 的吸附。通过同步辐射 X 射线光电子能谱分析和非初始密度泛函理论计算,解决了集群的非均相氧化问题。确定铂团簇上由团簇-支撑相互作用诱导的活性位点的可能性有望提高纳米催化剂设计的实验支持水平。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Unveiling Inequality of Atoms in Ultrasmall Pt Clusters: Oxygen Adsorption Limited to the Uppermost Atomic Layer

Unveiling Inequality of Atoms in Ultrasmall Pt Clusters: Oxygen Adsorption Limited to the Uppermost Atomic Layer
The concept of preferential atomic and molecular adsorption site is of primary relevance in heterogeneous catalysis. In the case of ultrasmall size-selected clusters, distinguishing the role played by each atom in a reaction is extremely challenging due to their reduced size and peculiar structures. Herein, it is revealed how the inequivalent atoms composing graphene-supported Pt12 and Pt13 clusters behave differently in the photoinduced dissociation of O2, with only those in the uppermost layer of the clusters being involved in the reaction. In this process, the epitaxial graphene support plays a fundamental active role: its corrugation and pinning induced by the presence of the clusters are crucial for defining the preferential adsorption site on the Pt atomic agglomerates, facilitating the lateral diffusion of physisorbed oxygen at a distance that induces its selective adsorption in the topmost layer of the clusters, and inducing an inhomogeneous charge distribution within the clusters which directly affects the O2 adsorption. The inhomogeneous oxidation of the clusters is resolved by means of synchrotron-based X-ray photoelectron spectroscopy and supported by ab initio density functional theory calculations. The possibility to identify the active sites on Pt clusters induced by cluster–support interactions has the potential to enhance the experimentally supported design of nanocatalysts.
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