Abstract
The last decade has witnessed tremendous progress in the development of computer simulation based on quantum mechanical description of the interactions between electrons and between electrons and atomic nuclei with electrode potentials taken into account–promoting the possibility to model electrocatalytic reactions. The cornerstone of this development was laid by the widely used computational hydrogen electrode method which involves a posteriori correction of standard constant charge first principles studies in solvent environment. The description of this technique and its contribution to our effort to understand electrocatalytic reactions on the active sites of metal-based nanoparticles are reviewed. The pathways and energetics of the relevant elementary reactions are presented. We also discussed a recent attempt in the literature to account for the inflow and outflow of electrons from the electrode as electrochemical reactions proceed, which has been greatly assisted by the development of density functional theory within the grand canonical framework. Going beyond the computational hydrogen electrode method by explicit incorporation of electrode potential within the calculations permits access to more detailed insights without requiring extra computational burden.
Highlights
Electrochemical fuel generation whose basic principle is to catalytically produce valuable chemical compounds from inert reactants under mild conditions is predicted to become an important component of future energy infrastructures [1,2,3,4,5,6]
We provided an overview of key concepts that enter into the theoretical modeling of electrochemistry
We first discussed the so-called zeroth-energy level protocol based on the electrochemical free-energy correction introduced by Norskov and co-workers which was used in large majority of simulations of heterogeneous electrocatalysis [11]
Summary
Electrochemical fuel generation whose basic principle is to catalytically produce valuable chemical compounds from inert reactants under mild conditions is predicted to become an important component of future energy infrastructures [1,2,3,4,5,6]. Aside from hard to measure geometric structures and electronic properties, the output from the simulation includes reaction pathways and free energy profiles Another key observable is the predicted trends that underlines the catalytic reactions, providing parameters for development of optimal catalysts and identifying fundamental and practical barriers that needed to be surmounted [5]. We first discussed the so-called zeroth-energy level protocol based on the electrochemical free-energy correction introduced by Norskov and co-workers which was used in large majority of simulations of heterogeneous electrocatalysis [11] In this approach, the influence of electrode voltage is included a posteriori to reaction energy differences that involve electron transfer with either a dielectric continuum or atomistic representation of the solvent. We discussed recent efforts to improve on the aforementioned approach by explicit inclusion of the electrochemical potential into the first-principles calculations [10]
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