In situ study of catalytic CO oxidation on ultrathin MgO film supported Pd nanoparticles by sum frequency generation: size and site effects.

Controlling the reactive sites of nanoparticles (NPs) is crucial to improve catalyst efficiency. In this work, sum-frequency generation is used to probe CO vibrational spectra on MgO(100) ultrathin film/Ag(100) supported Pd nanoparticles ranging from 3 to 6 nm in diameter and compared to those of coalesced Pd NPs and Pd(100) single crystals. We aim to demonstrate in situ the role played by active adsorption sites in the catalytic CO oxidation reactivity trends varying with the NP size. From ultrahigh vacuum to the mbar range and temperatures from 293 K to 340 K, our observations suggest that bridge sites are the main active sites for CO adsorption and catalytic oxidation. On Pd(100) single crystals at 293 K, CO oxidation predominates over CO poisoning at a pressure ratio of O2/CO greater than 300; on Pd NPs, both the site coordination due to NP geometry and MgO-induced Pd-Pd interatomic distance change impact the reactivity trend varying with size in different ways. Edge sites with low coordination are more reactive than facet sites, while facet sites with a smaller Pd-Pd atomic length are more reactive than that with a larger length. The interplay of both site and size effects gives rise to a non-monotonic reactivity trend of CO on the MgO(100) ultrathin film supported Pd NPs: the reactivity of Pd NPs increases for the smaller NP size side due to a higher edge/facet ratio and meanwhile increases for the larger NP size side due to the terrace facet with a smaller Pd-Pd atomic length at the NP surface and a lower diffusion barrier.

Probing Nanoparticle Geometry down to Subnanometer Size: The Benefits of Vibrational Spectroscopy.

Understanding the role of nanoparticle size and shape in the binding of molecules is very relevant for heterogeneous catalysis and molecular electronics. The geometry of Pd nanoparticles (NPs) has been studied from very small clusters containing 4 atoms up to large (>500 atoms), well-faceted NPs. Their geometry was retrieved by combining scanning tunneling microscopy and vibrational sum frequency generation (SFG) spectroscopy of adsorbed CO. SFG has been revealed to be highly sensitive to the geometry of NPs smaller than 100 atoms by identifying the nature of CO adsorption sites. NP growth could be followed layer by layer in the critical size range corresponding to the transition from a nonmetallic to a metallic state and to oscillations of CO adsorption energy. NP height remained at two Pd planes up to 30 atoms, and adsorption energy minima correspond to the completion of successive layers.

Identification of Active Sites in Oxidation Reaction from Real-Time Probing of Adsorbate Motion over Pd Nanoparticles.

Obtaining insight into the type of surface sites involved in a reaction is essential to understand catalytic mechanisms at the atomic level and a key for understanding selectivity in surface-catalyzed reactions. Here we use ultrafast broad-band vibrational spectroscopy to follow in real-time diffusion of CO molecules over a palladium nanoparticle surface toward an active site. Site-to-site hopping is triggered by laser excitation of electrons and followed in real-time from subpicosecond changes in the vibrational spectra. CO photoexcitation occurs in 400 fs and hopping from NP facets to edges follows within ∼1 ps. Kinetic modeling allows to quantify the contribution of different facet sites to the catalytic reaction. These results provide useful insights for understanding the mechanism of chemical reactions catalyzed by metal NPs.

Electron to Adsorbate Energy Transfer in Nanoparticles: Adsorption Site, Size, and Support Matter.

Confinement of hot electrons in metal nanoparticles (NPs) is expected to lead to increased reactivity in heterogeneous catalysis. NP size as well as support may influence molecule-NP coupling. Here, we use ultrafast nonlinear vibrational spectroscopy to follow energy transfer from hot electrons generated in Pd NP/MgO/Ag(100) to chemisorbed CO. Photoexcitation and photodesorption occur on an ultrashort time scale and are selective according to adsorption site. When the MgO layer is thick enough, it becomes NP size-dependent. Hot electron confinement within NPs is unfavorable for photodesorption, presumably because its dominant effect is to increase relaxation to phonons. An avenue of research is open where NP size and support thickness, photon energy, and molecular electronic structure will be tuned to obtain either molecular stability or reactivity in response to photon excitation.

Vibrational spectroscopy and dynamics of W(CO)6 in solid methane as a probe of lattice properties.

Methane solids present more than one accessible crystalline phase at low temperature at zero pressure. We trap W(CO)6 in CH4 and CD4 matrices between 8 and 35 K to probe the interaction between an impurity and its surrounding molecular solid under various physical conditions. Linear and nonlinear vibrational spectroscopies of W(CO)6 highlight different kinds of interaction and reveal new and remarkable signatures of the phase transition of methane. The structures in the absorption band of the antisymmetric CO stretching mode exhibit a clear modification at the transition between phase II and phase I in CH4 and motional narrowing is observed upon temperature increase. The vibrational dynamics of this mode is probed in stimulated photon echo experiments performed with a femtosecond IR laser. A short component around 10 ps is detected in the population relaxation lifetime in the high temperature phase of solid CH4 (phase I) and disappears at lower temperatures (phase II) where the vibrational lifetime is in the hundreds of ps. The analysis of the nonlinear time-resolved results suggests that the short component comes from a fast energy transfer between the vibrational excitation of the guest and the lattice in specific families of sites. Such fast transfers are observed in the case of W(CO)6 trapped in CD4 because of an energy overlap of the excitation of W(CO)6 and a lattice vibron. In solid CH4, even when these V-V transfers are not efficient, pure dephasing processes due to the molecular nature of the host occur: they are temperature dependent without a clear modification at the phase transition.

Vibrational perturbations of W(CO)6 trapped in a molecular lattice probed by linear and nonlinear spectroscopy.

Vibrational dynamics of the T1u CO stretching mode of tungsten hexacarbonyl is explored when the molecule is embedded in a nitrogen matrix at low temperature. Experiments combined infrared (IR) absorption spectroscopy and IR stimulated photon echoes at the femtosecond time scale. W(CO)6 is found to be trapped in two main families of sites differing by their symmetry (called hereafter Oh and D2h sites). In Oh sites, the vibrational coherence is strongly temperature dependent, exhibiting a coupling with librational phonons of the nitrogen lattice. Perturbation in D2h sites results in the splitting of the T1u band in three components. Each component is inhomogeneously broadened, with dephasing times in the tens of picoseconds, and is weakly coupled to the lattice phonons. Experiments in solid krypton are performed to compare the effect of atomic and diatomic host lattices. Dephasing time in Kr does not depend on temperature and remains in the hundreds of picoseconds, highlighting the molecular origin of the dephasing process in N2. Additionally, nonlinear signals show oscillations due to quantum beats and polarization interferences between different frequency components of the induced third order polarization, giving information, in particular, on the overtone vibrational transition.

Single-frequency Sb-based distributed-feedback lasers emitting at 2.3 microm above room temperature for application in tunable diode laser absorption spectroscopy.

GaInAsSb/GaAlAsSb/GaSb distributed-feedback (DFB) laser diodes based on a type I active region were fabricated by molecular beam epitaxy at the Centre d'Electronique et de Micro-Optoélectronique de Montpellier (CEM2). The DFB processing was done by Nanoplus Nanosystems and Technologies GmbH. The devices work in the continuous-wave regime above room temperature around an emission wavelength of 2.3 microm with a side-mode suppression ratio greater than 25 dB and as great as 10 mW of output power. The laser devices are fully characterized in terms of optical and electrical properties. Their tuning properties made them adaptable to tunable diode laser absorption spectroscopy because they exhibit more than 220 GHz of continuous tuning by temperature or current. The direct absorption of CH4 is demonstrated to be possible with high spectral selectivity.