Gas-phase reaction of CeVO₅⁺cluster ions with C₂H₄: the reactivity of cluster bonded peroxides

Abstract

Cerium-vanadium oxide cluster cations CeVO5(+) were generated by laser ablation, mass-selected using a quadrupole mass filter, thermalized through collisions with helium atoms, and then reacted with ethene molecules in a linear ion trap reactor. The cluster reactions have been characterized by time-of-flight mass spectrometry and density functional theory calculations. The CeVO5(+) cluster has a closed-shell electronic structure and contains a peroxide (O2(2-)) unit. The cluster bonded O2(2-) species is reactive enough to oxidize a C2H4 molecule to generate C2H4O2 that can be an acetic acid molecule. Atomic oxygen radicals (O(-)˙), superoxide radicals (O2(-)˙), and peroxides are the three common reactive oxygen species. The reactivity of cluster bonded O(-)˙ and O2(-)˙ radicals has been widely studied while the O2(2-) species were generally thought to be much less reactive or inert toward small molecules under thermal collision conditions. This work is among the first to report the reactivity of the peroxide unit on transition metal oxide clusters with hydrocarbon molecules, to the best of our knowledge.

Influence of preparation methods on the physicochemical properties and catalytic performance of MnO -CeO2 catalysts for NH3-SCR at low temperature

“…MnCe-CPM, and MnCe-SGM catalysts shifted to lower temperatures, which indicated that some electronic interactions existed between MnOx and CeO2 for these samples. This phenomenon is very similar to the findings of He et al[47,48] in cerium-gold oxide and cerium-vanadium oxide systems. Quantitative analysis of the H2-TPR data of the synthesized catalysts are summarized in Table2.…”

Adsorption of a single gold or silver atom on vanadium oxide clusters

“…DFT calculations were performed using the Gaussian 09 program 20 with the hybrid B3LYP functional. [21][22][23] This functional has been demonstrated by several research groups to produce reasonably good results for homonuclear V oxide clusters, [24][25][26][27][28][29][30][31] as well as some V-M (M = Si, P, Al, Ag, Ce) heteronuclear oxide clusters, [32][33][34][35][36][37][38][39] compared with various experimental results. Global optimization was carried out for all studied clusters by a homemade Fortran code 40 based on a genetic algorithm and DFT calculations.…”

Generation of free hydrogen atoms in thermal reaction of ethane with AuNbO 3 + cluster cations

“…It should be pointed out that the DFT calculated thermodynamics for reaction channels (4)-(6) is slightly inconsistent with the experimental observation that the reaction channel (4) is more favourable than channels (5) and (6) because reaction (4) is predicted to be the least exothermic among these three reactions. This can be due to systematic errors in calculating the bond energies by the adopted DFT functional [35,49].…”