PHOIBOS 150 2D-DLD

The hydrogenation of CO₂ to methanol is a viable alternative for reducing greenhouse gases net emissions as well as a route for hydrogen storage and transportation. In this context, the synthesis of active and selective catalysts is a relevant objective. In this work, we study the promotion of Pd with Ga and Zn in the hydrogenation of CO₂ to methanol at 800 kPa and 220–280 °C. Mono and intermetallic catalysts (Pd/SiO₂, PdGa/SiO₂ and Pd-Zn/SiO₂) were synthesized by incipient wetness impregnation with the aid of triethanolamine as an organic additive, obtaining similar average metal particle sizes (between 9 and 12 nm). Kinetic analysis reveals that the addition of Ga and Zn increases the turnover frequency for methanol formation by an order of magnitude without significant changes in the reaction rate of the reverse water-gas shift (r-WGS) which is a parallel undesired reaction. The selectivity to methanol (at 220 °C) thus increases from 3% for Pd/SiO₂ to 12% for Pd-Ga/SiO₂ and 30% for Pd-Zn/SiO2. XPS studies, Infrared analysis of CO adsorption, and XRD analyses show the presence of intermetallic phases Pd₂Ga and PdZn on the surface. The results suggest that Ga and Zn promote Pd, increasing its activity towards the synthesis of methanol, by creating more active sites for this reaction. These sites are likely formed by intermetallic compounds such as Pd₂Ga and PdZn.

The promotion of Ga on SiO₂ supported Cu in the hydrogenation of CO₂ to methanol at 800 kPa and 200–280 °C was investigated. Cu/SiO₂ and CuGa/SiO₂ catalysts were prepared by a water-in-oil microemulsion technique resulting in Cu clusters of 4–6.5 nm. It was found that Ga addition increased the methanol formation rate by an order of magnitude without significantly changing that for reverse water gas shift (RWGS). This trend is also evidenced by the decrease in the apparent activation barrier for methanol formation from 78 (for Cu/SiO₂) to 26–39 kJ mol⁻¹ when Ga was added, but not for RWGS (107–132 kJ mol⁻¹). Kinetic and in situ DRIFTS analyses revealed that formate intermediates are adsorbed on both Cu and Ga₂O₃ and that methoxy hydrogenation could be the rate determining step of methanol synthesis. In the case of RWGS, a zero order of CO formation with respect to H₂ concentration was consistent with a redox mechanism and with the reaction occurring predominantly on Cu sites. The results suggest that Ga promotes Cu increasing methanol selectivity, likely by creating new active sites for methanol formation without modifying its oxidation state, which under reaction conditions remains mostly metallic.

Understanding the physics of surface plasmons and related phenomena requires knowledge of the spatial, temporal, and spectral distributions of the total electromagnetic field excited within nanostructures and their interfaces, which reflects the electromagnetic mode excitation, confinement, propagation, and damping. We present a microscopic and spectroscopic study of the plasmonic response in single-crystalline Ag wires grown in situ on Si(001) substrates. Excitation of the plasmonic modes with broadly tunable (UV–IR) femtosecond laser pulses excites ultrafast multiphoton photoemission, whose spatial distribution is imaged with an aberration-corrected photoemission electron microscope, thereby providing a time-integrated map of the locally enhanced electromagnetic fields. We show by tuning the wavelength, polarization, and k-vector of the incident laser light that for a few micrometers long wires we can selectively excite either the propagating surface plasmon polariton modes or high-order multipolar resonances of the Ag/vacuum and Ag/Si interfaces. Moreover, upon tuning the excitation wavelength from the UV to the near-IR spectral regions, we find that the resonant plasmonic modes shift from the top of the wires to selvedge at the Ag/Si interface. Our results, supported by numerical simulations, provide a better understanding of the optical response of metal/semiconductor structures and guidance toward the design of polaritonic and nanophotonic devices with enhanced properties, as well as suggest mechanisms for plasmonically enhanced photocatalysis.

We investigate the electronic structure and photoexcitation dynamics of alkali atoms (Rb and Cs) chemisorbed on transition-metal Ru(0001) single-crystal surface by angle- and time-resolved multiphoton photoemission. Three- and four-photon photoemission (3PP and 4PP) spectroscopic features due to the σ and π resonances arising from the ns and np states of free alkali atoms are observed from ∼2 eV below the vacuum level in the zero-coverage limit. As the alkali coverage is increased to a maximum of 0.02 monolayers, the resonances are stabilized by formation of a surface dipole layer, but in contrast to alkali chemisorption on noble metals, both resonances form dispersive bands with nearly free-electron mass. Density functional theory calculations attribute the band formation to substrate-mediated interaction involving hybridization with the unoccupied d bands of the substrate. Time-resolved measurements quantify the phase and population relaxation times in the three-photon photoemission (3PP) process via the σ and π resonances. Differences between alkali-atom chemisorption on noble and transition metals are discussed.

Excitons, electron–hole pairs bound by the Coulomb potential, are the fundamental quasiparticles of coherent light–matter interaction relevant for processes such as photosynthesis and optoelectronics. The existence of excitons in semiconductors is well established. For metals, however, although implied by the quantum theory of the optical response, experimental manifestations of excitons are tenuous owing to screening of the Coulomb interaction taking place on timescales of a few femtoseconds. Here we present direct evidence for the dominant transient excitonic response at a Ag(111) surface, which precedes the full onset of screening of the Coulomb interaction, in the course of a three-photon photoemission process with 15 fs laser pulses. During this transient regime, electron–hole pair Coulomb interactions introduce coherent quasiparticle correlations beyond the single-particle description of the optics of metals that dominate the multi-photon photoemission process on the timescale of screening at a Ag(111) surface.

We show that atomically flat single SrO-terminated SrTiO3(001) substrates can be obtained through simple high-temperature treatment. Amplitude-modulation atomic force microscopy with phase-lag analysis and x-ray photoelectron spectroscopy, have been used to demonstrate that the ratio between the two chemical terminations can be tailored by choosing the annealing time. Moreover, the progressive SrO surface enrichment (up to 100%) is accompanied by a self-assembly process which results in the spatial separation at the nanoscale of both chemical terminations. We further demonstrate that this opens a interesting avenue for selective chemical reaction and growth of oxide nanostructures.