RESUMEN
A genetic algorithm is used with density functional theory to investigate the catalytic properties of 38- and 79-atom bimetallic core-shell nanoparticles for the oxygen reduction reaction. Each particle is represented by a two-gene chromosome that identifies its core and shell metals. The fitness of each particle is specified by how close the d-band level of the shell is to that of the Pt(111) surface, a catalyst known to be effective for oxygen reduction. The genetic algorithm starts by creating an initial population of random core-shell particles. The fittest particles are then bred and mutated to replace the least-fit particles in the population and form successive generations. The genetic algorithm iteratively refines the population of candidate catalysts more efficiently than Monte Carlo or random sampling, and we demonstrate how the average energy of the surface d-band can be tuned to that of Pt(111) by varying the core and shell metals. The binding of oxygen is a more direct measure of catalytic activity and is used to further investigate the fittest particles found by the genetic algorithm. The oxygen binding energy is found to vary linearly with the d-band level for particles with the same shell metal, but there is considerable variation in the trend across different shells. Several particles with oxygen binding energies similar to Pt(111) have already been investigated experimentally and found to be active for oxygen reduction. In this work, many other candidates are identified.
Asunto(s)
Algoritmos , Catálisis , Nanopartículas/química , Metales/química , Modelos Moleculares , Oxidación-Reducción , Oxígeno/química , Platino (Metal)/químicaRESUMEN
Experimental results supported by density functional theory calculations show carbonate formation and reaction on atomic oxygen precovered Au(111). Oxygen mixing is observed in temperature-programmed desorption measurements when a Au(111) precovered with 16O is exposed to isotopically labeled CO2 (C18O2). The presence of 16O18O is attributed to surface carbonate formation and decomposition at surface temperatures ranging from 77-400 K and initial oxygen coverages ranging from 0.18-2.1 ML. A reaction probability on the order of 10(-4) and an activation energy of -0.15+/- 0.08 eV are estimated for this reaction.
RESUMEN
Water-oxygen interactions and CO oxidation by water on the oxygen-precovered Au(111) surface were studied by using molecular beam scattering techniques, temperature-programmed desorption (TPD), and density functional theory (DFT) calculations. Water thermally desorbs from the clean Au(111) surface with a peak temperature of approximately 155 K; however, on a surface with preadsorbed atomic oxygen, a second water desorption peak appears at approximately 175 K. DFT calculations suggest that hydroxyl formation and recombination are responsible for this higher temperature desorption feature. TPD spectra support this interpretation by showing oxygen scrambling between water and adsorbed oxygen adatoms upon heating the surface. In further support of these experimental findings, DFT calculations indicate rapid diffusion of surface hydroxyl groups at temperatures as low as 75 K. Regarding the oxidation of carbon monoxide, if a C (16)O beam impinges on a Au(111) surface covered with both atomic oxygen ( (16)O) and isotopically labeled water (H 2 (18)O), both C (16)O (16)O and C (16)O (18)O are produced, even at surface temperatures as low as 77 K. Similar experiments performed by impinging a C (16)O beam on a Au(111) surface covered with isotopic oxygen ( (18)O) and deuterated water (D 2 (16)O) also produce both C (16)O (16)O and C (16)O (18)O but less than that produced by using (16)O and H 2 (18)O. These results unambiguously show the direct involvement and promoting role of water in CO oxidation on oxygen-covered Au(111) at low temperatures. On the basis of our experimental results and DFT calculations, we propose that water dissociates to form hydroxyls (OH and OD), and these hydroxyls react with CO to produce CO 2. Differences in water-oxygen interactions and oxygen scrambling were observed between (18)O/H 2 (16)O and (18)O/D 2 (16)O, the latter producing less scrambling. Similar differences were also observed in water reactivity toward CO oxidation, in which less CO 2 was produced with (16)O/D 2 (16)O than with (16)O/H 2 (16)O. These differences are likely due to primary kinetic isotope effects due to the differences in O-H and O-D bond energies.