Density Functional Theory Study on the Metal–Support Interaction between Ru Cluster and Anatase TiO₂(101) Surface

Abstract

Density functional theory (DFT) calculations were carried out to study the nucleation and growth mechanism of Ru clusters on the TiO 2 (101) surface by using supported Ru n (n = 1−10, 20, 22) cluster models to understand the metal−support interaction and the resulting catalytic performance toward CO oxidation. The results show that the Ru n cluster prefers a 3D geometry when n ≥ 4 and that the Ru−TiO 2 interface is predominantly composed of Ru−O and Ti−O bonds. Calculation studies based on the density of states (DOS), Hirshfeld charge analysis, and electron deformation density (EDD) demonstrate that the electronic interaction is mainly localized at the Ru−TiO 2 interface through the electron transfer via the Ru−O bond. Additionally, the investigation on catalytic behavior of Ru n /TiO 2 toward CO oxidation reveals the largely enhanced catalytic activity of the supported Ru n clusters, which originates from the significant reduction of the activation barrier as a result of the electron transfer from Ru to TiO 2 .

Stability and mobility of supported Nin (n = 1–10) clusters on ZrO2(111) and YSZ(111) surfaces: a density functional theory study

“…Aer relaxation, the atoms adopted a Ni(111)-facetted tetrahedron shape on the zirconia surface. Similar studies 20,49 have shown the preference of aggregation of metal clusters on oxide surfaces. For example, Zhang et al 49 have shown that for n $ 4 Ru n adopts a 3-D geometry on TiO 2 (101), whereas Rajesh et al 20 have shown that the aggregation of Au atoms is more favourable than wetting the Al 2 O 3 surface.…”

“…Similar studies 20,49 have shown the preference of aggregation of metal clusters on oxide surfaces. For example, Zhang et al 49 have shown that for n $ 4 Ru n adopts a 3-D geometry on TiO 2 (101), whereas Rajesh et al 20 have shown that the aggregation of Au atoms is more favourable than wetting the Al 2 O 3 surface. The analysis of the interfacial distances in the Ni 6 /ZrO 2 (111) system shows that each Ni atom is at $1.9Å from its nearest O u neighbour.…”

Subnanometric Hybrid Pd-M(OH)2, M = Ni, Co, Clusters in Zeolites as Highly Efficient Nanocatalysts for Hydrogen Generation

“…For the transition metal atom/clusters deposited on oxide/hydroxide supports, the model of a heterogeneous catalyst is adopted by a supported metal cluster on the oxide/hydroxide surfaces, which has been generally accepted for understanding the metal-support interaction in many theoretical studies. [48][49][50][51] Here, a periodic surface of Pd-Ni(OH) 2 was modeled by a two-layer Ni(OH) 2 (001) slab with a (5 3 5) unit cell and a threelayer Pd cluster containing 19 Pd atoms placed on this slab ( Figure S38).…”

Adsorption of Ruthenium Atoms and Clusters on Anatase TiO2 and Tetragonal ZrO2(101) Surfaces: A Comparative DFT Study

“…E ads is defined as: 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 11 the results found by Zhang et al on the same system. 62 The adsorption mode is characterized by a covalent-polar bond with partial depletion of the electronic charge from Ru which, according to the Bader analysis, has a charge q = +0.6 |e|, Table 2. However, formation of Ti 3+ ions is not observed as shown by both the pDOS curves, Figure 4(b) and (c), and the spin density plots, Figure 5(a).…”