Revisiting the Electrified Pt(111)/Water Interfaces through an Affordable Double-Reference Ab Initio Approach

Abstract

The electrified solid–liquid interface plays an essential role in many renewable energy-related applications, including hydrogen production and utilization. Limitations in computational modeling of the electrified solid–liquid interface have held back the understanding of its properties at the atomic-scale level. In this study, we applied the grand canonical density functional theory (GC-DFT) combined with a hybrid implicit/explicit solvation model to reinvestigate the widely studied electrified platinum-water interface affordably. The calculated double-layer capacitances of the Pt(111)–water interface over the applied bias potential closely match the experimental and previous theoretical data from expensive ab initio molecular dynamics simulations. The structural analysis of the interface models reveals that the applied bias potential can significantly affect the Pt(111)–water atomic interface configurations. The orientation of the water molecules next to the Pt(111) surface is vital for correctly describing the potential of zero charge (PZC) and capacitance. Additionally, the GC-DFT results confirm that the absorption of the hydrogen atom under applied bias potential can significantly affect the electrified interfacial properties. The presented affordable GC-DFT approach, therefore, offers an efficient and accurate means to enhance the understanding of electrified solid–liquid interfaces.

Pt single crystal surfaces in electrochemistry and electrocatalysis

“…Recently, there have been numerous efforts to obtain a detailed picture of the interphase in contact with the Pt(111) electrode to reproduce experimental results and to obtain valuable insights into the reactivity of platinum electrodes using GC-DFT calculations including explicit water layers and ab initio molecular dynamics (AIMD). 111–115 Those results highlight the importance of the local hydrogen-bond network in the structure and properties of the double layer, which affects the electrocatalysis. 105 GC-DFT 111 and AIMD 116 have been able to reproduce the capacity maximum around the pzfc, and the existence of an ion distribution that does not follow the mean-field Poisson–Boltzmann distribution.…”

“…111–115 Those results highlight the importance of the local hydrogen-bond network in the structure and properties of the double layer, which affects the electrocatalysis. 105 GC-DFT 111 and AIMD 116 have been able to reproduce the capacity maximum around the pzfc, and the existence of an ion distribution that does not follow the mean-field Poisson–Boltzmann distribution. 43…”