(Digital Presentation) Characterization of Ultrafast Dynamics of Refractory Metal Nanoparticles of Interest as Photocatalysts

Plasmonic noble metal nanoparticles are of interest as photocatalysts for several reasons, including a very large absorption cross section and the creation of a greatly enhanced evanescent electromagnetic field at the surface of the nanoparticles when excited at the plasmon resonance. Furthermore, the plasmon resonance is tunable over a wide wavelength range as a function of the size, shape, and composition of the nanoparticles. When these properties are combined with the known photocatalytic activity of noble metals for technologically important targets such as solar fuels, it is not surprising that these nanoparticle systems are widely studied. Noble metals do, however, possess a weakness in that they can be easily melted upon photoexcitation, due to the fact that noble metals dissipate absorbed photon energy efficiently through ultrafast electron-phonon coupling, in roughly one picosecond, to produce heat. As a result, the study of new classes of plasmonic materials, such as refractory metals, with much higher melting points than noble metals is growing rapidly. While there are still challenges in the size-selective synthesis of refractory metal nanoparticles, characterization efforts on these materials are of strong interest. We report here a study on the time-resolved spectroscopy of electron-phonon coupling in refractory metal nanoparticles. There are very significant variations in the efficiency and time-scales of electron-phonon coupling in refractory metal nanoparticles as compared to noble metal nanoparticles. Furthermore, due to the fact that many refractory metals are oxidized under ambient conditions to create a thin oxide layer on the surface of the nanoparticles, these materials also demonstrate dynamics related to electron injection from the metal to the oxide layer that noble metals do not show. Far from being a negative, the added electron injection dynamics offer new opportunities for photocatalysis that we discuss. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.