An Overview of Significant Achievements in Ruthenium-Based Molecular Water Oxidation Catalysis

Fossil fuels (coal, oil, natural gas) are becoming increasingly disfavored as long-term energy options due to concerns of scarcity and environmental consequences (e.g., release of anthropogenic CO₂). Hydrogen gas, on the other hand, has gained popularity as a clean-burning fuel because the only byproduct from its reaction with O₂ is H₂O. In recent decades, hydrogen derived from water splitting has been a topic of extensive research. The bottleneck of the water splitting reaction is the difficult water oxidation step (2H₂O → O₂ + 4H⁺ + 4e^-), which requires an effective and robust catalyst to overcome its high kinetic barrier. Research in water oxidation by molecular ruthenium catalysts enjoys a rich history spanning nearly 40 years. As the diversity of novel ligands continues to widen, the relationship between ligand geometry or electronics, and catalyst activity is undoubtedly becoming clearer. The present review highlights, in the authors' opinion, some of the most impactful discoveries in the field and explores the evolution of ligand design that has led to the current state of the art.