Expanding the frontiers of electrocatalysis: advanced theoretical methods for water splitting

Abstract Electrochemical water splitting, which encompasses the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), offers a promising route for sustainable hydrogen production. The development of efficient and cost-effective electrocatalysts is crucial for advancing this technology, especially given the reliance on expensive transition metals, such as Pt and Ir, in traditional catalysts. This review highlights recent advances in the design and optimization of electrocatalysts, focusing on density functional theory (DFT) as a key tool for understanding and improving catalytic performance in the HER and OER. We begin by exploring DFT-based approaches for evaluating catalytic activity under both acidic and alkaline conditions. The review then shifts to a material-oriented perspective, showcasing key catalyst materials and the theoretical strategies employed to enhance their performance. In addition, we discuss scaling relationships that exist between binding energies and electronic structures through the use of charge-density analysis and d -band theory. Advanced concepts, such as the effects of adsorbate coverage, solvation, and applied potential on catalytic behavior, are also discussed. We finally focus on integrating machine learning (ML) with DFT to enable high-throughput screening and accelerate the discovery of novel water-splitting catalysts. This comprehensive review underscores the pivotal role that DFT plays in advancing electrocatalyst design and highlights its potential for shaping the future of sustainable hydrogen production. Graphical Abstract