Photoexcitation of Fe₃ O Nodes in MOF Drives Water Oxidation at pH=1 When Ru Catalyst Is Present

Artificial photosynthesis strives to convert the energy of sunlight into sustainable, eco-friendly solar fuels. However, systems with light-driven water oxidation reaction (WOR) at pH=1 are rare. Broadly used [Ru(bpy)₃ ]²⁺ (bpy=2,2'-bipyridine) photosensitizer has a fixed +1.23 V potential which is insufficient to drive most water oxidation catalysts (WOCs) in acid, while Fe₂ O₃ , featuring the highly oxidizing holes, is not stable at low pH. Here, the key examples of Fe-based metal-organic framework (MOF) water oxidation photoelectrocatalysts active at pH=1 are presented. Fe-MIL-126 and Fe MOF-dcbpy structures were formed with 4,4'-biphenyl dicarboxylate (bpdc), 2,2'-bipyridine-5,5'-dicarboxylate (dcbpy) linkers and their mixtures. Presence of dcbpy linkers allows integration of metal-based catalysts via coordination to 2,2'-bipyridine fragments. Fe-based MOFs were doped with Ru-based precursors to achieve highly active MOFs bearing [Ru(bpy)(dcbpy)(H₂ O)₂ ]²⁺ WOC. Materials were analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra-red (FTIR) spectroscopy, resonance Raman, X-ray absorption spectroscopy, fs optical pump-probe, electron paramagnetic resonance (EPR), diffuse reflectance and electric conductivity measurements and were modeled by band structure calculations. It is shown that under reaction conditions, Fe^III and Ru^III oxidation states are present, indicating rate-limiting electron transfer in MOF. Fe₃ O nodes emerge as photosensitizers able to drive prolonged O₂ evolution in acid. Further developments are possible via MOF's linker modification for enhanced light absorption, electrical conductivity, reduced MOF solubility in acid, Ru-WOC modification for faster WOC catalysis, or Ru-WOC substitution to 3d metal-based systems. The findings give further insight for development of light-driven water splitting systems based on Earth-abundant metals.