Physical and electronic interaction at interface of materials grants an opportunity to explore a unique chemical pathway owing to its structural anisotropy and high surface energy. Thus, an efficient and reliable first-principles simulation must be provided for both in silico understanding and a priori prediction of interfacial interaction. In that sense, density functional theory (DFT) provides us with plausible (semi)local approximation for explaining electronic structure of materials yet still lacks an accurate description of interaction occurring at interfaces, especially van der Waals interaction. In this thesis, we suggest a van der Waals correction method for the DFT that can accurately describe interfacial interaction of diverse systems. In addition, we discuss different electrocatalytic selectivity and acitivity that are attributed to the interfacial interaction with 2D materials based on the DFT simulations.