RESUMO
An experimental methodology for a mechanistic analysis of gas phase chemical reactions is presented in the context of structure-reactivity relationships of metal oxide clusters relevant to photocatalysis. The spectroscopic approach is demonstrated with the investigation of the photoinduced oxygenation of propene on the V(4)O(11)(-) cluster, where the thermal activation and subsequent photoreaction are deduced with the information from (i) the temperature dependency of the aggregation kinetics in the propene-seeded helium atmosphere of an ion-trap reactor; (ii) the fluence dependency in the yield of different product channels of the photoreaction and (iii) the intensity dependency in the fragmentation of neutral reaction products that are probed via in situ multi-photon ionization. For the thermal reaction, selective hydrogen abstraction from the allylic position of propene accompanied by the linkage to the cluster at the dioxo moiety is postulated as the mechanism in the aggregation of propene on the V(4)O(11)(-) cluster. In accordance with an insightful neutralization-reionization study (Schröder et al., J. Mass. Spectrom., 2010, 301, 84), the subsequent photoinduced reaction is defined by an allylic oxidation in the formation of acrolein from the initial allyloxy radical photoproduct. The relevance of the observed selectivity is discussed in view of the electronic structure and bond motifs offered by high valence oxide systems such as the V(4)O(11)(-) cluster.
RESUMO
The anionic V4O11 cluster is presented as a gas-phase system of low dimensionality for modeling surface activation of molecular oxygen and the reactivity toward unsaturated hydrocarbons. Together with the charged cluster aggregates and fragments taking part in the reaction, neutral reactant and product species are monitored via multiphoton ionization for the first time within the instrumentation of tandem mass spectrometry and ion trap reactors. This novel approach allows for a comprehensive analysis of the photoinduced oxygen transfer reaction to propene within the defined aggregate complex [V4O11 x C3H6]- that simulates coadsorption and activation under fully controlled conditions.
RESUMO
A practicable and economic method for the generation and full characterization of laser pulses ranging down to sub 7 fs duration with energies spanning the full microJ domain is presented. The method utilizes a self-induced and self-guiding filamentation of titanium-sapphire based, amplified pulses in air for spectral broadening, a standard chirp mirror compression scheme and transient grating frequency resolved optical gating for determining the spectral phase over the full visible to near infrared range. In this manner, few-cycle laser pulses with a high quality in the spatial beam profile have been generated in an robust arrangement with a minimal amount of standard optical components for their full characterization. The optical scheme demonstrates an uncomplicated, versatile access to this regime of pulsed laser radiation accompanied by a comprehensive analysis.
