Thermal and Femtosecond Laser-Induced CO2-Surface Chemistry on Supported Iron-Oxide Based Nanoparticle Surfaces under UHV

Abstract

The thesis has been presented in two parts. The 1st part of the thesis focuses on the fundamental understanding of room temperature CO2 adsorption on iron-oxide based NP surfaces. The 2nd part describes the understanding of an interesting catalytic reaction dynamics, namely of metalized energetic molecules. The content of the thesis is presented in the following way. In Chapter 2, fabrication, structural elucidation and CO2 surface chemistry of supported iron-oxide (α-Fe2O3) NPs are discussed. In Chapter 3, the same on the supported Fe-Pd-oxide(shell)@Pd(core) NP surfaces is presented where the bimetallization by introducing Pd+2 doping in iron-oxide (α-Fe2O3) NPs, leads to CO2 adsorption at the room temperature. A periodic density functional theory (DFT) results for the CO2 adsorption on the model pristine α-Fe2O3(0001) and on the model Pd+2 doped α-Fe2O3(0001) surfaces are discussed in Chapter 4. In Chapter 5, femtosecond pulse induced chemistry of CO2 on Pd(core)@Fe-Pd-oxide(shell) NP surfaces is discussed. In Chapter 6 I have presented conical intersection-mediated nonadiabatic chemical dynamics of a simple analogue nitramine (containing one N-NO2 energetic group) molecule, dimethylnitramine (DMNA) and its complex with an iron atom (DMNA-Fe). Finally, in Chapter 7, general conclusions and future directions are presented