Photocatalytic Conversion of CO 2 to Hydrocarbon Fuels via Plasmon-Enhanced Absorption and Metallic Interband Transitions

A systematic study of the mechanisms of Au nanoparticle/TiO 2 -catalyzed photoreduction of CO 2 and water vapor is carried out over a wide range of wavelengths. When the photon energy matches the plasmon resonance of the Au nanoparticles (free carrier absorption), which is in the visible range (532 nm), we observe a 24-fold enhancement in the photocatalytic activity because of the intense local electromagnetic fields created by the surface plasmons of the Au nanoparticles. These intense electromagnetic fields enhance sub-bandgap absorption in the TiO 2, thereby enhancing the photocatalytic activity in the visible range. When the photon energy is high enough to excite d band electronic transitions in the Au, in the UV range (254 nm), a different mechanism occurs resulting in the production of additional reaction products, including C 2 H 6, CH 3 OH, and HCHO. This occurs because the energy of the d band excited electrons lies above the redox potentials of the additional reaction products CO 2 /C 2 H 6, CO 2 /CH 3 OH, and CO 2 /HCHO. We model the plasmon excitation at the Au nanoparticle-TiO 2 interface using finite difference time domain (FDTD) simulations, which provides a rigorous analysis of the electric fields and charge at the Au nanoparticle-TiO 2 interface.