It has been a long challenge to understand the equilibrium and the dynamic phenomena (e.g. chemical reactions) at the electrode/electrolyte interface in a unified theoretical framework. In this talk, we will introduce our methodology development based on the periodic first-principles calculations integrated with modified-Poisson�Boltzmann electrostatics, namely, DFT/CM-MPB method. In the past few years, we have applied the method to understand the nature of electrochemical double layer and the catalytic reaction at the interface, as those related to electro and photo catalytic reactions. The double layer properties of a series of metal electrodes and adsorbate-covered electrode, such as the potential of zero charge and the differential capacitance, can now calculated from theory and a good agreement between theoretical values and experimental data is achieved. The theoretical method is also applied to probe the mechanism, particularly the kinetics of the catalytic reactions at the solid-liquid interface. The Tafel kinetics can be calculated and the potential-dependent behavior of different reactions can now rationalized and classified from the atomic level. 1  . Zhao, W.-N.; Liu, Z.-P.* 'Mechanism and Active Site of Photocatalytic Water Splitting on Titania in Aqueous Surroundings', Chem. Sci., 2014, in press 2  . Li, Y.-F.; Liu, Z.-P.* �Particle Size, Shape and Activity for Photocatalysis on Titania Anatase Nanoparticles in Aqueous Surroundings�J. Am. Chem. Soc. 2011, 133,15743 3  . Shang, C.; Liu, Z.-P.* �Origin and Activity of Gold Nanoparticle as Aerobic Oxidation Catalyst in Aqueous Solution�J. Am. Chem. Soc. 2011, 133,9938 4  . Fang, Y.-H.; Liu, Z.-P.* �Mechanism and Tafel Lines of Electro-oxidation of Water to Oxygen on RuO2(110) � J. Am. Chem. Soc. 2010, 132, 182145  . Li, Y.-F.; Liu, Z.-P.*; Liu, L.;Gao, W. �Mechanism and Activity of Photocatalytic Oxygen Evolution on Titania Anatase in Aqueous Surroundings �J. Am. Chem. Soc. 2010, 132, 130086 . Wang, H.-F.; Liu, Z.-P.* �Comprehensive Mechanism and Structure-Sensitivity of Ethanol Oxidation on Platinum: New Transition-State Searching Method for Resolving Complex Reaction Network� J. Am. Chem. Soc. 2008, 130,10996

Theoretical modeling of electrode/electrolyte interface from ?rst-principles periodic continuum solvation (DFT/CM-MPB) method

248th National Meeting (2014)

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