Abstract
In this contribution we will present a detailed methodology for the elucidation of the following aspects of the thermodynamic properties of hydrated metal oxide nanoparticles from high-resolution, low-temperature inelastic neutron scattering (INS) data: (i) the isochoric heat capacity and entropy of the hydration layers both chemi- and physisorbed to the particle surface; (ii) the magnetic contribution to the heat capacity of the nanoparticles. This will include the calculation of the vibrational density of states (VDOS) from the raw INS spectra, and the subsequent extraction of the thermodynamic data from the VDOS. This technique will be described in terms of a worked example namely, cobalt oxide (Co3O4 and CoO).
To complement this evaluation of the physical properties of metal oxide nanoparticle systems, we will emphasise the importance of high-resolution, high-energy INS for the determination of the structure and dynamics of the water species, namely molecular (H2O) and dissociated water (OH, hydroxyl), confined to the oxide surfaces. For this component of the chapter we will focus on INS investigations of hydrated isostructural rutile (a-TiO2) and cassiterite (SnO2) nanoparticles.
We will complete this discussion of nanoparticle analysis by including an appraisal of the INS instrumentation employed in such studies with particular focus on TOSCA [ISIS, Rutherford Appleton Laboratory (RAL), U.K.] and the newly developed spectrometer SEQUOIA [SNS, Oak Ridge National Laboratory (ORNL), U.S.A].
