NO Adsorption on Ag/Pt（110）-（1×2） Bimetallic Surfaces： Unexpected Formation of Nitrite/nitrate Surface Species

NO adsorption on Ag/Pt（110）-（1×2） bimetallic surfaces at room temperature was investigated by means of Auger electron spectroscopy, X-ray photoelectron spectroscopy and thermal desorption spectroscopy. An unexpected formation of nitrite/nitrate surface species on Ag/Pt（110）-（1 ×2） bimetallic surfaces is observed, then decompose at elevated temperatures to form N2. However, such nitrite/nitrate surface species do not form on clean Pt（110） and Ag-Pt alloy surfaces upon NO exposure at room temperature. The formation of nitrite/nitrate surface species on Ag/Pt（110）-（1×2） bimetallic surfaces is attributed to high reactivity of highly coordination-unsaturated Ag clusters and the synergetic effect between Ag clusters and Pt substrate.

Density Functional Theory Study of the Adsorption of C_2H_2 on the Cu/Pt(111) Bimetallic Surfaces

We applied periodic density-functional theory to investigate the adsorption of C2H2 on the Cu/Pt bimetallic and monometallic surfaces, including Cu-Pt-Pt and Pt--Cu-Pt representing the monolayer Cu on the Pt surface and subsurface Cu in the Pt surface, respectively. For the Pt（111） and Pt-Cu-Pt surfaces, C2H2 is preferentially a 3-fold “parallel-bridge” configuration, and a ＂p-bridge＂ structure exists above the Cu（111） and Cu-Pt-Pt surfaces. The adsorption energy of C2H2 on these surfaces decreases in the order Pt（111） 〉 Cu-Pt-Pt 〉 Pt-Cu-Pt 〉 Cu（11）. The analysis of density of states, charge, and vibrational frequencies showed obviously weakening of the adsorbed C-C bond and high sp2 character on the carbon atom. Furthermore, when the top-layer compositions are equal, the nearer the EF d-band center is, the larger the C2H2 adsorption energy will be.

Adsorption of HCN on Ni/Pt(111)Bimetallic Surfaces Investigated with Density Functional Theory Method

We applied periodic density-functional theory to investigate the adsorption of HCN on x Ni@Pt（111） bimetallic surfaces（x = 1~4）. The results have been compared with those obtained on pure Ni（111） and Pt（111） surfaces. For all bimetallic surfaces,HCN is preferentially tilted with the CN bond parallel to the surface,and adsorption energies increase with an increasing number of layer Ni atoms on the surface. The adsorption energies of HCN on all bimetallic surfaces are larger than that on the Pt（111） surface,whereas the adsorption energies of HCN on 3Ni@Pt（111） and 4Ni@Pt（111） are larger than that on the Ni（111） surface,indicating that the introduction of Ni to the Pt catalyst could increase the activity of bimetallic catalyst in the hydrogenation reaction for nitriles. Larger adsorption energy of HCN leads to a longer C–N bond length and a smaller CN vibrational frequency. The analysis of Bader charge and vibrational frequencies showed obvious weakening of the adsorbed C–N bond and an indication of sp2 hybridization of both carbon and nitrogen atoms.

Influence of PtMo Structure and Composition on the Adsorption Energies, Adsorption Site and Vibrational Frequency of Carbon Monoxide

Density functional theory periodic slab calculations were carded out for CO adsorption on a series of Mo modified Pt（111） surfaces to provide an insight into the interaction between CO and doped metal surface, an important issue in CO oxidation as well as in promotion and poisoning effects of catalysis. The modification of adsorption properties with respect to those of adsorption on the pure Mo（110） and Pt（111） is described in terms of changes in the adsorption energies, adsorption sites and vibrational properties occurring upon alloying. We believe that the present DFT calculations can provide important information into optimal alloy composition for CO-tolerance, which is not easily obtained by experimental methods.