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<p>The growing global demand for sustainable and clean energy has intensified research efforts toward artificial photosynthesis as a viable strategy for solar fuel production. Among the various approaches, water splitting into hydrogen and oxygen represents a promising pathway for converting solar energy into storable chemical energy. However, the water oxidation reaction (WOR), a four-electron and four-proton process, remains the principal kinetic and thermodynamic bottleneck in artificial photosynthetic systems. Inspired by the natural oxygen-evolving complex (OEC) of Photosystem II, which contains a Mn<sub>4</sub>CaO<sub>5</sub> cluster, manganese-based molecular catalysts have emerged as attractive candidates for water oxidation due to their earth abundance, low cost, rich redox chemistry, and biological relevance. This review critically discusses representative and mechanistically informative Mn-based homogeneous electrocatalysts (mononuclear and binuclear) that have significantly contributed to the understanding and development of manganese-mediated electrocatalytic water oxidation. Emphasis is placed on ligand design strategies, including corroles, porphyrins, pyridinophanes, carboxamido frameworks, and non-heme N-donor systems, and their role in stabilizing high-valent Mn(IV/V)-oxo intermediates essential for O–O bond formation. The mechanistic pathways for oxygen evolution, particularly water nucleophilic attack (WNA), interaction of two metal-oxo units, and proton-coupled electron transfer (PCET), are critically discussed under electrochemical conditions. Various methods employed to evaluate catalytic performance, chemical, photochemical, and electrochemical approaches are summarized, with particular attention to key parameters such as overpotential, turnover number (TON), turnover frequency (TOF), Faradaic efficiency, and pH dependence. Recent advances demonstrate that subtle modifications in ligand electronics, steric, and π-delocalization significantly influence catalytic activity, overpotential, and mechanistic pathways. Overall, this review highlights the progress, mechanistic understanding, and future prospects of manganese-based molecular electrocatalysts as sustainable alternatives to noble-metal systems for artificial photosynthesis.</p>

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Nature-Inspired Artificial Photosynthesis: Manganese-Based Molecular Electrocatalysts for Homogeneous Water Oxidation

  • 期刊论文

  • 发表日期：

    2026年7月8日

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  • Karunamay Majee,
  • Ritika Kubba,
  • Gandharve Kumar,
  • Abhishek Maurya

摘要

The growing global demand for sustainable and clean energy has intensified research efforts toward artificial photosynthesis as a viable strategy for solar fuel production. Among the various approaches, water splitting into hydrogen and oxygen represents a promising pathway for converting solar energy into storable chemical energy. However, the water oxidation reaction (WOR), a four-electron and four-proton process, remains the principal kinetic and thermodynamic bottleneck in artificial photosynthetic systems. Inspired by the natural oxygen-evolving complex (OEC) of Photosystem II, which contains a Mn4CaO5 cluster, manganese-based molecular catalysts have emerged as attractive candidates for water oxidation due to their earth abundance, low cost, rich redox chemistry, and biological relevance. This review critically discusses representative and mechanistically informative Mn-based homogeneous electrocatalysts (mononuclear and binuclear) that have significantly contributed to the understanding and development of manganese-mediated electrocatalytic water oxidation. Emphasis is placed on ligand design strategies, including corroles, porphyrins, pyridinophanes, carboxamido frameworks, and non-heme N-donor systems, and their role in stabilizing high-valent Mn(IV/V)-oxo intermediates essential for O–O bond formation. The mechanistic pathways for oxygen evolution, particularly water nucleophilic attack (WNA), interaction of two metal-oxo units, and proton-coupled electron transfer (PCET), are critically discussed under electrochemical conditions. Various methods employed to evaluate catalytic performance, chemical, photochemical, and electrochemical approaches are summarized, with particular attention to key parameters such as overpotential, turnover number (TON), turnover frequency (TOF), Faradaic efficiency, and pH dependence. Recent advances demonstrate that subtle modifications in ligand electronics, steric, and π-delocalization significantly influence catalytic activity, overpotential, and mechanistic pathways. Overall, this review highlights the progress, mechanistic understanding, and future prospects of manganese-based molecular electrocatalysts as sustainable alternatives to noble-metal systems for artificial photosynthesis.