Converting solar energy into useful chemical bonds via photocatalysis is a growing field aimed at addressing global challenges. The research disclosed describes heterogeneous photocatalysis as a nanophotoelectrochemical cell as photocatalysts enable both reduction and oxidation reactions using the local charge separation of photo-excited carriers. Herein, experimental and theoretical results of nanoscale electrolysis of water on the surface of CrOx/Pt/SrTiO3 showed that ohmic losses are negligible when the anode and cathode are within nanometer distances from each other. Additionally, increasing the photocatalytic rate of water splitting by increasing the light intensity demonstrated that pH gradients can still form at the nanoscale. These pH gradients can be minimized by the incorporation of buffers. Typically, photocatalysts decorated with noble-metal nanoparticles can be used for overall water splitting, but generally suffer from low yields due to the water-forming back reaction. The unwanted water-forming back reaction was successfully suppressed by coating Pt nanoparticles on the surface of SrTiO3 with a 2nm CrOx layer that block O2 gas from reaching the surface of the Pt nanoparticle. The back reaction can also be suppressed without the use of a protective layer material by changing the intrinsic nature of the Pt nanoparticle from a metallic state to an oxidized state. The Pt nanoparticles were able to maintain an oxidized state by reducing the particle size below 2 nm. Oxidized Pt particles are less likely to bind to H2, O2, and CO gas, unlike metallic Pt, thereby making it selective for hydrogen generation. Finally, CdS was found to be perform the direct trifluoromethylation of heteroarenes in a single step as opposed to the current multi-step synthetic procedures. The trifluoromethylation of organic compounds is relevant to the field of medicinal chemistry for the synthesis of pharmaceutical drugs. By improving overall water splitting via photocatalysis significantly, artificial photosynthesis may be achieved leading to a solution to the global energy security dilemma. By improving photoredox catalysis of organic compounds via photocatalysis, high value organic compounds (such as pharmaceuticals) can be synthesized more readily under milder conditions.