Electrochemistry
A copper porphyrin oxidizes water at low overpotential
Open access · cc by · source: Europe PMC
A molecular Cu(II) porphyrin evolves O2 at 300–440 mV overpotential in neutral phosphate buffer with >93% faradaic efficiency.
Key findings
At pH 7 the catalyst shows a strong water-oxidation wave with η = 300 mV (DPV foot) and 440 mV (CV half-peak) and >93% FE for O2. Pourbaix slope −0.029 V/pH implies a 2e−/1H+ step. In acid it also makes H2O2 (45% FE). The first oxidation is the porphyrin radical, not Cu(III).
Methodology
Authors ran CV, DPV, and controlled-potential electrolysis of a copper(II) porphyrin in phosphate buffers, quantified O2 and H2O2, and used spectroscopy to assign a ligand-centered cation radical as the first oxidation.
Limitations
A device-level solar-to-fuel efficiency and long-term PEM electrolyzer durability are not reported; H2O2 selectivity in acid is only 45%.
How this study connects
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