Photocatalytic Conversion of CO<sub>2</sub> to Hydrocarbon Fuels via Plasmon-Enhanced Absorption and Metallic Interband Transitions HouWenbo HungWei Hsuan PavaskarPrathamesh GoeppertAlain AykolMehmet CroninStephen B. 2011 A systematic study of the mechanisms of Au nanoparticle/TiO<sub>2</sub>-catalyzed photoreduction of CO<sub>2</sub> 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<sub>2</sub>, 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<sub>2</sub>H<sub>6</sub>, CH<sub>3</sub>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<sub>2</sub>/C<sub>2</sub>H<sub>6</sub>, CO<sub>2</sub>/CH<sub>3</sub>OH, and CO<sub>2</sub>/HCHO. We model the plasmon excitation at the Au nanoparticle-TiO<sub>2</sub> interface using finite difference time domain (FDTD) simulations, which provides a rigorous analysis of the electric fields and charge at the Au nanoparticle-TiO<sub>2</sub> interface.