A DFT study of the NO dissociation on gold surfaces doped with transition metals

Abstract

The NO dissociation on a series of doped gold surfaces (type TM n @Au(111) or TM n @Au(110), with TM n = Ni, Ir, Rh, or Ag and referring n to the number of dopant atoms per unit cell) was investigated through periodic density functional theory calculations. Generally, doping of Au (111) and Au(110) matrices was found to strengthen the interaction with NO species, with the exception of Ag, and was found to increase the energy barrier for dissociation, with the exception of Ni on Au(111). The calculations suggest that the NO dissociation is only possible in the case of the Ir@Au(110) bimetallic surface but only at high temperatures. The increase of the contents of Ir on Au(110) was found to improve significantly the catalytic activity of gold towards the NO dissociation (E act = ∼1 eV). Nevertheless, this energy barrier is almost the double of that calculated for NO dissociation on pure Ir(110). However, mixing the two most interesting dopant atoms resulted in a catalyst model of the type Ir@Ni(110) that was found to decrease the energy barrier to values close to those calculated for pure Ir surfaces, i.e., ∼0.4 eV, and at the same time the dissociation reaction became mildly exothermic.

Density functional theory study of CO-induced segregation in gold-based alloys

“…Adsorbate-induced segregation has previously been observed in gold-based alloys, where strong binding of an adsorbate such CO [23,30], NO [31][32], O and O 2 [21][22] to the metal with the highest cohesive energy causes segregation of that metal to the surface the opposite of what is observed in vacuum. In a recent work, we have reported oxygen-induced segregation of 10 group transition metal impurities M (M = Pt, Pd, and Ni) alloyed with gold.…”

First principle calculations of nitric oxide on metallic Pt (111) and Pt (100), and bimetallic Au/Pt (111) and Au/Pt (100) surfaces

“…The post-processing of the nitric oxides has stimulated extensive studies of the adsorption and decomposition of NO x (x = 1-3) molecules on surfaces of catalysts. The adsorption between the nitric oxides (especially NO) and bimetallic surfaces has been studied by numerous experimental [17][18][19] and theoretical investigations [20][21][22][23]. These studies mainly focused on (1 1 1) surface, while the (1 0 0) surface is paid less attention.…”

Catalysis of Cu Cluster for NO Reduction by CO: Theoretical Insight into the Reaction Mechanism

“…Similar catalysts, Au atom (or cluster) doped on M (M = Ni, Rh, Pd, Ag, or Ir), were applied to NO–CO reaction. 13,14 In these studies, the dissociative NO adsorption was proposed as an important initial step like in the NO–CO reaction by Rh, Pt, and Pd catalysts. 2,3,5,6,8,9 Also, Ag nanoscale particles were experimentally reported to be active for NO decomposition.…”