Dual Cocatalysts in TiO 2 Photocatalysis

Semiconductor-based photocatalysis attracts wide attention because of its ability to directly utilize solar energy for production of solar fuels, such as hydrogen and hydrocarbon fuels and for degradation of various pollutants. However, the efficiency of photocatalytic reactions remains low due to the fast electron-hole recombination and low light utilization. Therefore, enormous efforts have been undertaken to solve these problems. Particularly, properly engineered heterojunction photocatalysts are shown to be able to possess higher photocatalytic activity because of spatial separation of photogenerated electron-hole pairs. Here, the basic principles of various heterojunction photocatalysts are systematically discussed. Recent efforts toward the development of heterojunction photocatalysts for various photocatalytic applications are also presented and appraised. Finally, a brief summary and perspectives on the challenges and future directions in the area of heterojunction photocatalysts are also provided.

The identification of the active sites in heterogeneous catalysis requires a combination of surface sensitive methods and reactivity studies. We determined the active site for hydrogen evolution, a reaction catalyzed by precious metals, on nanoparticulate molybdenum disulfide (MoS2) by atomically resolving the surface of this catalyst before measuring electrochemical activity in solution. By preparing MoS2 nanoparticles of different sizes, we systematically varied the distribution of surface sites on MoS2 nanoparticles on Au(111), which we quantified with scanning tunneling microscopy. Electrocatalytic activity measurements for hydrogen evolution correlate linearly with the number of edge sites on the MoS2 catalyst.