We measured first- and second-order Raman scattering in cubic and hexagonal boron nitride using excitation energies in the visible and in the UV. The nonresonant first-order Raman susceptibilities for cubic and hexagonal BN are 1 and $10{\mathrm{\AA }}^2$, respectively. Raman scattering is thus very powerful in detecting the hexagonal phase in mixed thin boron nitride films. In cubic BN the constant Raman sucseptibility in the visible and the UV is due to its indirect band gap. For hexagonal BN a Raman enhancement is found at $5.4\mathrm{eV}$. It is well explained by the energy dependence of the dielectric function of hexagonal BN. The second-order spectrum of cubic boron nitride is in excellent agreement with first-principles calculations of the phonon density of states. In hexagonal BN the overbending of the LO phonon is $\approx 100{\mathrm{cm}}^{-1}$, five times larger than in graphite.

Identification of active sites in heterogeneous metal catalysts is critical for understanding the reaction mechanism at the molecular level and for designing more efficient catalysts. Because of their structural flexibility, subnanometric metal catalysts, including single atoms and clusters with a few atoms, can exhibit dynamic structural evolution when interacting with substrate molecules, making it difficult to determine the catalytically active sites. In this work, Pt catalysts containing selected types of Pt entities (from single atoms to clusters and nanoparticles) have been prepared, and their evolution has been followed, while they were reacting in a variety of heterogeneous catalytic reactions, including selective hydrogenation reactions, CO oxidation, dehydrogenation of propane, and photocatalytic H₂ evolution reaction. By in situ X-ray absorption spectroscopy, in situ IR spectroscopy, and high-resolution electron microscopy techniques, we will show that some characterization techniques carried out in an inadequate way can introduce confusion on the interpretation of coordination environment of highly dispersed Pt species. Finally, the combination of catalytic reactivity and in situ characterization techniques shows that, depending on the catalyst–reactant interaction and metal–support interaction, singly dispersed metal atoms can rapidly evolve into metal clusters or nanoparticles, being the working active sites for those abovementioned heterogeneous reactions.