The infrared absorption and Raman scattering spectra were measured for the metallotriph- enylcorroles （MTPCs, M=Cu, Co, Ni, Mn）. The ground-state structures and vibrational spectra of MTPCs have been calculated with the density functional theory. The observed Raman and IR bands have been assigned based on the calculation results. Due to the symmetry lowering, the vibrational spectra of MTPCs are much more complex than metal- loporphyrins, and several skeletal modes are found strongly coupled to the phenyl vibrations. The relationship between the Raman/IR frequencies and the structures of TPC ring is in-vestigated. It is found that the vibrations involving the Cα^I Cα^I stretch and CαCm stretchare sensitive to the size of corrole core. In particular, the frequency of v5, which is assigned to Cα^I Cα^I stretch in coupling with the CαCm symmetric stretch, increases linearly with the decrease of the corrole core-sizes and may be used as a mark band to evaluate the structural change of the metallocorroles.
Supported gold nanoparticle catalysts show extraordinarily high activity in many reactions. While the relative poor thermal stability of Au nanoparticles against sintering at elevated temperatures severely limits their practical applications. Here atomic layer deposition （ALD） of TiO2 and Al2O3 was performed to deposit an Au/TiO2 catalyst with precise thickness con-trol, and the thermal stability was investigated. We surprisingly found that sub-nanometer-thick Al2O3 overcoat can su ciently inhibit the aggregation of Au particles up to 600 C in oxygen. On the other hand, the enhancement of Au nanoparticle stability by TiO2 overcoat is very limited. Di use reffectance infrared Fourier transform spectroscopy （DRIFTS） of CO chemisorption and X-ray photoelectron spectroscopy measurements both con rmed the ALD overcoat on Au particles surface and suggested that the presence of TiO2 and Al2O3 ALD overcoat on Au nanoparticles does not considerably change the electronic properties of Au nanoparticles. The catalytic activities of the Al2O3 overcoated Au/TiO2 catalysts in CO oxidation increased as increasing calcination temperature, which suggests that the embed-ded Au nanoparticles become more accessible for catalytic function after high temperature treatment, consistent with our DRIFTS CO chemisorption results.
