Over the past decade, tremendous advances have made on first principles based modeling of interfacial electrochemistry, which permit not only the mechanistic understanding of the basic thermodynamics and kinetics of complex electrocatalytic reaction networks and but also computational design of new alloy electrocatalysts. [1] Nevertheless, it is still a big challenge for the modeling of electrified interfaces with explicit double layer features (i.e. hydrogen bonds, solvent, electrode potential), which in some instances, yield completely unexpected physical and catalytic properties. For alkaline electrocatalysis at bi-functional three-phase boundaries of ultra-thin 3d transition metal (hydroxy)oxide films, Pt substrates, and the surrounding water,[2,3] it is more challenging, as the interface structures are largely unknown and the large errors in standard DFT calculations on the description of strongly-correlated (hydroxy)oxides. These have significantly impeded the design of new bi-functional catalysts with further improved performance.

In this talk, I will briefly review the methodologies we have recently developed, including a synergistic strategy towards highly accurate prediction of Pourbaix diagram of transition metal (hydroxy)oxides,[4] a simple scheme for fast screening of stable single layer transition metal (hydroxy)oxide film/metal interfaces under electrochemical conditions. Next, using hydrogen evolution reaction as an example, I will demonstrate how these techniques can be applied to understand the steady state, the active phases and the catalytic mechanism of mono- and bi-functional catalysts. Finally, I will show these understandings can be used to design new bi-functional catalysts with improved performances.

If time permit, I will introduce some of our recent developments on explicitly modeling of electrified electrode/electrode interfaces with full double layer features.

[1] J. Greeley, I. E. L. Stephens, A. S. Bondarenko, T. P. Johansson, H. A. Hansen, T. F. Jaramillo, J. Rossmeisl, I. Chorkendorff, J. K. Nørskov, Nat. Chem. 2009, 1, 552-556.

[2] Subbaraman, R.; Stamenkovic, V.; Markovic, N. et al, Science 2011, 334, 1256.

[3] Subbaraman, R.; Greeley, J.; Stamenkovic, V.; Markovic, N. et al, Nat Mater 2012, 11, 550

[4] Z. Zeng, M. K. Y. Chan, Z.-J. Zhao, J. Kubal, D. Fan, J. Greeley, J. Phys. Chem. C 2015, 119, 18177