Probe molecule chemisorption-low energy ion scattering study of surface active sites present in the orthorhombic Mo-V-(Te-Nb)-O catalysts for propane (amm)oxidation

Methanol and allyl alcohol chemisorption and surface reaction in combination with low energy ion scattering (LEIS) were employed to determine the outermost surface compositions and chemical nature of active surface sites present on the orthorhombic (M1) Mo-V-O and Mo-V-Te-Nb-O phases. These orthorhombic phases exhibited vastly different behavior in propane (amm)oxidation reactions and, therefore, represented highly promising model systems for the study of the surface active sites. The LEIS data for the Mo-V-Te-Nb-O catalyst indicated surface depletion for V (-23%) and Mo (-27%), and enrichments for Nb (+55%) and Te (+165%) with respect to its bulk composition. Only minor changes in the topmost surface composition were observed for this catalyst under the conditions of the LEIS experiments at 400 degrees C, which is a typical temperature employed in these propane transformation reactions. These findings strongly suggested that the bulk orthorhombic Mo-V-Te-Nb-O structure may function as a support for the unique active and selective surface monolayer in propane (amm)oxidation. Moreover, direct evidence was obtained that the topmost surface VO(x) sites in the orthorhombic Mo-V-Te-Nb-O catalyst were preferentially covered by chemisorbed allyloxy species, whereas methanol was a significantly less discriminating probe molecule. The surface TeO(x) and NbO(x) sites on the Mo-V-Te-Nb-O catalyst were unable to chemisorb these probe molecules to the same extent as the VO(x) and MoO(x) sites. Our findings suggested that different surface locations for V(5+) ions in the orthorhombic Mo-V-O and Mo-V-Te-Nb-O catalysts may be primarily responsible for vastly different catalytic behavior exhibited by the Mo-V-O and Mo-V-Te-Nb-O phases. Although the proposed isolated V(5+) pentagonal bipyramidal sites in the orthorhombic Mo-V-O phase may be capable of converting propane to propylene with modest selectivity, the selective 8-electron transformation of propane to acrylic acid and acrylonitrile may require the presence of several surface VO(x) redox sites lining the entrances to the hexagonal and heptagonal channels of the orthorhombic Mo-V-Te-Nb-O phase. The study of allyl alcohol oxidation over the Mo-V-O and Mo-V-Te-Nb-O catalysts further suggested that water plays a critical role during the oxidation of acrolein intermediate to acrylic acid over the orthorhombic (M1 phase) Mo-V-Te-Nb-O catalysts. Finally, the present study strongly indicated that chemical probe chemisorption combined with low energy ion scattering (LEIS) is a novel and highly promising surface characterization technique for the investigation of the active surface sites present in the bulk mixed metal oxides.     

Laplacian energy of a graph

Let G be a graph with n vertices and m edges. Let λ₁, λ₂, … , λ_n be the eigenvalues of the adjacency matrix of G, and let μ₁, μ₂, … , μ_n be the eigenvalues of the Laplacian matrix of G. An earlier much studied quantity is the energy of the graph G. We now define and investigate the Laplacian energy as . There is a great deal of analogy between the properties of E(G) and LE(G), but also some significant differences.     

Two-dimensional nonlinear beam shaping

We develop a technique for two-dimensional arbitrary wavefront shaping in quadratic nonlinear crystals by using binary nonlinear computer generated holograms. The method is based on transverse illumination of a binary modulated nonlinear photonic crystal, where the phase matching is partially satisfied through the nonlinear Raman-Nath process. We demonstrate the method experimentally showing a conversion of a fundamental Gaussian beam pump light into three Hermite-Gaussian and three Laguerre-Gaussian beams in the second harmonic. Two-dimensional binary nonlinear computer generated holograms open wide possibilities in the field of nonlinear beam shaping and mode conversion.