Catalytic Reactions on Pd–Au Bimetallic Model Catalysts

ConspectusThe enhanced catalytic activity of Pd–Au catalysts originates from ensemble effects related to the local composition of Pd and Au. The study of Pd–Au planar model catalysts in an ultrahigh vacuum (UHV) environment allows the observation of molecular level catalytic reactions between the Pd–Au surface and target molecules. Recently, there has been progress in understanding the behavior of simple molecules (H2, O2, CO, etc.) employing UHV surface science techniques, the results of which can be applied not only to heterogeneous catalysis but also to electro- and photochemical catalysis.Employing UHV methods in the investigation of Pd–Au model catalysts has shown that single Pd atoms can dissociatively adsorb H2 molecules. The recombinative desorption temperature of H2 varies with Pd ensemble size, which allows the use of H2 as a probe molecule for quantifying surface composition. In particular, H2 desorption from Pd–Au interface sites (or small Pd ensembles) is observed from 150–300 K, which is between the H2 desorption temperature from pure Au (∼110 K) and Pd (∼350 K) surfaces. When the Pd ensembles are large enough to form Pd(111)-like islands, H2 desorption occurs from 300–400 K, as with pure Pd surfaces. The different H2 desorption behavior, which depends on Pd ensemble size, has also been applied to the analysis of dehydrogenation mechanisms for potential liquid storage mediums for H2, namely formic acid and ethanol. In both cases, the Pd–Au interface is the main reaction site for generating H2 from formic acid and ethanol with less overall decomposition of the two molecules (compared to pure Pd).The chemistry behind O2 activation has also been informed through the control of Pd ensembles on a gold model catalyst for acetaldehyde and ethanol oxidation reactions under UHV conditions. O2 molecules molecularly adsorbed on continuous Pd clusters can be dissociated into O adatoms above 180 K. This O2 activation process is improved by coadsorbed H2O molecules. It is also possible to directly (through a precursor mechanism) introduce O adatoms on the Pd–Au surface by exposure to O2 at 300 K. The quantity of dissociatively adsorbed O adatoms is proportional to the Pd coverage. However, the O adatoms are more reactive on a less Pd covered surface, especially at the Pd–Au interface sites, which can initiate CO oxidation at temperatures as low as 140 K. Acetaldehyde molecules can be selectively oxidized to acetic acid on the Pd–Au surface with O adatoms, in which the selectivity toward acetic acid originates from preventing the decarboxylation of acetate species. Moreover, the O adatoms on the Pd–Au surface accelerate ethanol dehydrogenation, which causes the increase in acetaldehyde production. Hydrogen is continuously abstracted from the formed acetaldehyde and remaining ethanol molecules, and they ultimately combine as ethyl acetate on the Pd–Au surface.Using Pd–Au model catalysts under UHV conditions allows the discovery of molecular level mechanistic details regarding the catalytic behavior of H and O adatoms with other molecules. We also expect that these findings will be applicable regarding other chemistry on Pd–Au catalysts.