在石墨烯负载的亚纳米级氧化铁簇中观察到的最高氧化态。

The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters.

作者信息

Perco Deborah, Loi Federico, Bignardi Luca, Sbuelz Luca, Lacovig Paolo, Tosi Ezequiel, Lizzit Silvano, Kartouzian Aras, Heiz Ueli, Baraldi Alessandro

机构信息

Department of Physics, University of Trieste, Via Valerio 2, 34127, Trieste, Italy.

Elettra - Sincrotrone Trieste, AREA Science Park, 34149, Trieste, Italy.

出版信息

Commun Chem. 2023 Apr 3;6(1):61. doi: 10.1038/s42004-023-00865-x.

Abstract

Size-selected iron oxide nanoclusters are outstanding candidates for technological-oriented applications due to their high efficiency-to-cost ratio. However, despite many theoretical studies, experimental works on their oxidation mechanism are still limited to gas-phase clusters. Herein we investigate the oxidation of graphene-supported size-selected Fe clusters by means of high-resolution X-ray Photoelectron Spectroscopy. We show a dependency of the core electron Fe 2p binding energy of metallic and oxidized clusters on the cluster size. Binding energies are also linked to chemical reactivity through the asymmetry parameter which is related to electron density of states at the Fermi energy. Upon oxidation, iron atoms in clusters reach the oxidation state Fe(II) and the absence of other oxidation states indicates a Fe-to-O ratio close to 1:1, in agreement with previous theoretical calculations and gas-phase experiments. Such knowledge can provide a basis for a better understanding of the behavior of iron oxide nanoclusters as supported catalysts.

摘要

尺寸选择的氧化铁纳米团簇因其高性价比而成为面向技术应用的杰出候选物。然而,尽管有许多理论研究,但关于其氧化机制的实验工作仍仅限于气相团簇。在此,我们通过高分辨率X射线光电子能谱研究了石墨烯负载的尺寸选择的铁团簇的氧化。我们展示了金属态和氧化态团簇的核心电子Fe 2p结合能对团簇尺寸的依赖性。结合能还通过与费米能级处的态密度相关的不对称参数与化学反应性相关联。氧化后,团簇中的铁原子达到Fe(II)氧化态,且不存在其他氧化态表明Fe与O的比例接近1:1,这与先前的理论计算和气相实验一致。这些知识可为更好地理解作为负载型催化剂的氧化铁纳米团簇的行为提供基础。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0f47/10070315/fba54cf19974/42004_2023_865_Fig1_HTML.jpg

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