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

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‐Al 2 O 3 (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/Al 2 O 3 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/Al 2 O 3 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.