A water-soluble dinuclear copper electrocatalyst, [Cu(oxpn)Cu(OH)2] for both water reduction and oxidation

• Cu(oxpn)Cu(OH)21 can catalyze both water oxidation and reduction to provide O2 and H2, respectively.
• Water reduction occurs with a TOF of 1383 moles h−1 at an overpotential of 0.689 V (pH 7.0).
• Water oxidation occurs at an overpotential of 0.289 V to give O2 with a TOF of ∼6.7 s−1.
• Sustained water reduction catalysis to give H2 over a 72 h electrolysis period with 97.4% Faradaic yield.

ABSTRACTThe reaction of N,N′-bis(3-aminopropyl) oxamido ligand (oxpn) and Cu(OH)2 affords a dinuclear copper(II) complex, Cu(oxpn)Cu(OH)21, a molecular electrocatalyst for both water reduction and oxidation. Water oxidation occurs at an overpotential of 0.289 V with a turnover frequency (TOF) of ∼6.7 s−1. Water reduction occurs with a TOF of 1383 moles of hydrogen per mole of catalyst per hour at an overpotential of 0.689 V (pH 7.0). Sustained water reduction catalysis occurs at glassy carbon (GC) to give H2 over a 72 h electrolysis period with 97.4% Faradaic yield and no observable decomposition of the catalyst.

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