DFT-guided design of two-dimensional materials for hydrogen production and storage

Abstract

Density Functional Theory (DFT) has emerged as a cornerstone of modern computational materials science, offering atomistic-level insights and predictive capabilities for material properties that are often difficult to access experimentally. When integrated with complementary approaches such as Molecular Dynamics (MD) and Monte Carlo (MC) simulations, DFT enables a robust multiscale framework for the rational design of advanced nanostructured materials. This review provides a comprehensive and coherent overview of DFT-driven investigations of two-dimensional (2D) materials for hydrogen production and storage. Particular attention is devoted to adsorption mechanisms, electronic structure engineering, charge transfer phenomena, and catalytic reaction pathways associated with hydrogen evolution reactions (HER) and hydrogen uptake. Emerging 2D materials—including phosphorene, Be₂C, Al₄C₃, and GeC—as well as carbon-rich 2D carbides are analyzed in detail due to their remarkable physicochemical properties. Key descriptors such as adsorption energy, activation barriers, and density of states (DOS) are discussed as fundamental criteria for evaluating catalytic activity and storage performance. Furthermore, coupling DFT with MD and Kinetic Monte Carlo (KMC) simulations provides valuable insights into thermal stability, hydrogen diffusion, and operational behavior under realistic conditions. In addition, porous adsorbents such as metal–organic frameworks (MOFs), including MOF-5 and IRMOF-10, are examined for hydrogen storage applications. This work highlights how theoretical modeling significantly accelerates the discovery and optimization of materials for sustainable hydrogen energy technologies.