Confinement Effects of Two‐Dimensional Surfaces on Water Adsorption and Dissociation over Pt(111)

Abstract It has been established that the confined space created by stacking a two dimensional (2D) surface atop a metal catalyst serves as a nano‐reactor. According to recent research, when a graphene (Gr) overlayer encloses a catalyst from above, the activation barrier for the water dissociation reaction, a process with major industrial significance, decreases. In order to investigate how the effect of confinement varies among different two‐dimensional (2D) materials, we study the adsorption and dissociation barriers of water molecule on (111) under graphene, hexagonal boron nitride (h‐BN), and heptazine‐based graphitic carbon nitride (g‐C 3 N 4 ) layers using density functional theory calculations. Our findings reveal that the strength of adsorption does not decrease consistently with a reduction in the height of the 2D overlayer. Furthermore, a smaller barrier is not always the consequence of poorer adsorption of the reactant. We also examine the effect of confinement on the shape of the reaction path, on the frequencies of vibrational modes, and on the rate constants derived using the harmonic transition state theory. Overall, all three 2D surfaces cause a decrease in barrier height and a weakening of adsorption, though to differing degrees due to a mix of mechanical, geometric and electronic variables.