Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches.

Increased demand for a carbon-neutral sustainable energy scheme augmented by climatic threats motivates the design and exploration of novel approaches that reserve intermittent solar energy in the form of chemical bonds in molecules and materials. In this context, inspired by biological processes, artificial photosynthesis has garnered significant attention as a promising solution to convert solar power into chemical fuels from abundantly found HO. Among the two redox half-reactions in artificial photosynthesis, the four-electron oxidation of water according to 2HO → O + 4H + 4e comprises the major bottleneck and is a severe impediment toward sustainable energy production. As such, devising new catalytic platforms, with traditional concepts of molecular, materials and biological catalysis and capable of integrating the functional architectures of the natural oxygen-evolving complex in photosystem II would certainly be a value-addition toward this objective. In this review, we discuss the progress in construction of ideal water oxidation catalysts (WOCs), starting with the ingenuity of the biological design with earth-abundant transition metal ions, which then diverges into molecular, supramolecular and hybrid approaches, blurring any existing chemical or conceptual boundaries. We focus on the geometric, electronic, and mechanistic understanding of state-of-the-art homogeneous transition-metal containing molecular WOCs and summarize the limiting factors such as choice of ligands and predominance of environmentally unrewarding and expensive noble-metals, necessity of high-valency on metal, thermodynamic instability of intermediates, and reversibility of reactions that create challenges in construction of robust and efficient water oxidation catalyst. We highlight how judicious heterogenization of atom-efficient molecular WOCs in supramolecular and hybrid approaches put forth promising avenues to alleviate the existing problems in molecular catalysis, albeit retaining their fascinating intrinsic reactivities. Taken together, our overview is expected to provide guiding principles on opportunities, challenges, and crucial factors for designing novel water oxidation catalysts based on a synergy between conventional and contemporary methodologies that will incite the expansion of the domain of artificial photosynthesis.