Combined Experimental and Periodic DFT Study of the Size Dependence of Adsorption Properties of Oxide‐Supported Metal Nanoclusters: A Case of NO on Ni/Al2O3

IF 1.6 4区化学 Q4 CHEMISTRY, PHYSICAL

Surface and Interface Analysis Pub Date : 2024-08-22 DOI:10.1002/sia.7350

Tamerlan T. Magkoev, Yong Men, Reza Behjatmanesh‐Ardakani, Mohammadreza Elahifard, Vladimir T. Abaev, Petrakis Chalikidi, Taymuraz T. Magkoev, Oleg G. Ashkhotov

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引用次数: 0

Abstract

It is demonstrated by means of ultra high vacuum (UHV) surface‐sensitive techniques and periodic density functional theory (DFT) calculations that the electronic and NO− adsorption properties of nanosized Ni clusters deposited onto the α‐Al2O3 (0001) surface significantly depend upon the size of the cluster. The properties of the Ni cluster of the size of 2 nm and lower are predominantly determined by the formation of the Ni/Al2O3 interface bond notably polarized towards the oxide. As a result, the metal cluster acquires a net positive charge manifested by the bond strengthening of adsorbed NO compared to the bulk Ni substrate. With the increasing size of the cluster, the Ni/Al2O3 interfacial bond depolarizes due to the growing of lateral Ni–Ni interaction. With a mean coverage of Ni on the alumina surface exceeding 0.25 equivalent monolayers, their properties in terms of adsorption behavior of NO resemble those that are characteristic for the bulk Ni substrate. Such a size dependence offers an opportunity to tune the properties of metal clusters and the metal/oxide system as a whole, for example, to achieve the required electronic and adsorption‐reaction properties.

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氧化物支撑金属纳米团簇吸附特性的尺寸依赖性实验与周期 DFT 结合研究：氮氧化物在 Ni/Al2O3 上的吸附情况

通过超高真空（UHV）表面敏感技术和周期性密度泛函理论（DFT）计算，证明了沉积在 αAl2O3 (0001) 表面的纳米级镍团簇的电子和氮氧化物吸附特性明显取决于团簇的尺寸。尺寸为 2 nm 及以下的镍簇的特性主要取决于镍/Al2O3 界面键的形成，该键明显向氧化物极化。因此，金属簇获得了净正电荷，表现为与块状镍基底相比，吸附 NO 的键增强。随着金属簇大小的增加，镍/Al2O3 界面键由于镍-镍横向相互作用的增加而去极化。由于氧化铝表面镍的平均覆盖率超过 0.25 个等效单层，它们在吸附 NO 方面的特性与块状镍基底的特性相似。这种尺寸依赖性为调整金属团簇和整个金属/氧化物系统的特性提供了机会，例如，实现所需的电子和吸附反应特性。

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来源期刊

Surface and Interface Analysis 化学-物理化学

CiteScore

3.30

自引率

5.90%

发文量

130

审稿时长

4.4 months

期刊介绍： Surface and Interface Analysis is devoted to the publication of papers dealing with the development and application of techniques for the characterization of surfaces, interfaces and thin films. Papers dealing with standardization and quantification are particularly welcome, and also those which deal with the application of these techniques to industrial problems. Papers dealing with the purely theoretical aspects of the technique will also be considered. Review articles will be published; prior consultation with one of the Editors is advised in these cases. Papers must clearly be of scientific value in the field and will be submitted to two independent referees. Contributions must be in English and must not have been published elsewhere, and authors must agree not to communicate the same material for publication to any other journal. Authors are invited to submit their papers for publication to John Watts (UK only), Jose Sanz (Rest of Europe), John T. Grant (all non-European countries, except Japan) or R. Shimizu (Japan only).