Oxidative Addition of Methane and Reductive Elimination of Ethane and Hydrogen on Surfaces: From Pure Metals to Single Atom Alloys.

Oxidative addition of CH4 to the catalyst surface produces CH3 and H. If the CH3 species generated on the surface couple with each other, reductive elimination of C2H6 may be achieved. Similarly, H's could couple to form H2. This is the outline of nonoxidative coupling of methane (NOCM). It is difficult to achieve this reaction on a typical Pt catalyst surface. This is because methane is overoxidized and coking occurs. In this study, the authors approach this problem from a molecular aspect, relying on organometallic or complex chemistry concepts. Diagrams obtained by extending the concepts of the Walsh diagram to surface reactions are used extensively. C-H bond activation, i.e., oxidative addition, and C-C and H-H bond formation, i.e., reductive elimination, on metal catalyst surfaces are thoroughly discussed from the point of view of orbital theory. The density functional theory method for structural optimization and accurate energy calculations and the extended Hückel method for detailed analysis of crystal orbital changes and interactions play complementary roles. Limitations of monometallic catalysts are noted. Therefore, a rational design of single atom alloy (SAA) catalysts is attempted. As a result, the effectiveness of the Pt1/Au(111) SAA catalyst for NOCM is theoretically proposed. On such an SAA surface, one would expect to find a single Pt monatomic site in a sea of inert Au atoms. This is desirable for both inhibiting overoxidation and promoting reductive elimination.