The electronic properties of Au clusters on CeO₂ (110) surface with and without O-defects

Abstract

We use density functional theory with Hubbard corrections (DFT+U) to understand the local electronic properties of Au adatom and Au 2 dimer adsorption on the CeO 2 (110) surface. We show that, based on the initial geometries, we can observe Au species in . We present a detailed discussion using Bader charge analysis and partial density of states to support our observations. We also discuss the influence of solvent on the adsorption of Au adatoms adsorbed on top of an O-vacancy, which shows interesting geometrical and electronic properties.

A computational investigation of the adsorption of small copper clusters on the CeO2(110) surface

“…Therefore, in this study we have only investigated the configurations which have the most negative Cu adsorption energies based on the DFT+U calculations, as listed in ESI Table 3, and compared the structures and energetics without (DFT+U) and with the van der Waals dispersion term (DFT+U+D3). We find that for each of the nine configurations investigated, the inclusion of the D3 term only makes the adsorption energies slightly more negative (maximum difference less than 0.23 eV) which agrees with the previous work 47,49,50 .…”

“…In Case3, one Ce 3+ is a surface NN, while the other one is a surface NNN. Calculated oxygen vacancy formation energies are in the range of 0.98-1.43 eV, as reported in Table 4, which are slightly lower than those from previous work (1.54-2.69 eV) 2, 24, 44-46 , because of a more negative O 2 binding energy of -9.863 eV (bond length 1.233 Å) used in our work24,47 (ESI Section 1.5). The well-known error of overbinding O 2 using GGA/LDA DFT and PAW potentials24,46 , as well as different computational parameters used (e.g.…”

“…We note from previous studies that the inclusion of dispersion corrections in the DFT+U based calculations has a minimal effect on the local geometrical and electronic properties 47,49,50 . Therefore, in this study we have only investigated the configurations which have the most negative Cu adsorption energies based on the DFT+U calculations, as listed in ESI Table 3, and compared the structures and energetics without (DFT+U) and with the van der Waals dispersion term (DFT+U+D3).…”

Toward an Atomic-Level Understanding of Ceria-Based Catalysts: When Experiment and Theory Go Hand in Hand

“…Because ceria directly participates in the catalytic reaction, it is of great interest to further explore the influence of the support on the mode of operation. In addition to above-mentioned facet-dependent differences in the ease with which oxygen vacancies can be created, the exposed facet may affect the interactions between ceria and the supported gold ,, as well as between gas-phase molecules (CO, H 2 O) and the catalyst surface. ,,, Recently, we have examined structure–activity relations for CO oxidation over Au/rods (CeO 2 (110), CeO 2 (100)) and Au/cubes (CeO 2 (100)) using combined operando Raman/UV–vis spectra and DFT calculations, with the former showing higher low-temperature CO oxidation activity. In the following text, we will first illustrate important aspects of the facet-dependent behavior and then include our previous work on polycrystalline ceria supported gold in the discussion. ,, …”

The influence of oxygen vacancy and Ce3+ ion positions on the properties of small gold clusters supported on CeO2−x(111)

“…13 The Aun/CeO2-X system has been the subject of several computational studies although most of them focussed on very small clusters. [14][15][16][17][18] Chutia et al 27 studied single gold atoms and demonstrated that electron transfer to the gold occurred over vacancies. Zhang et al investigated the structures and properties of Au clusters with up to 11 atoms, but all their structures were built under the precondition that one of the Au atoms is located at a vacancy site.…”