Electrochemical-driven water splitting catalyzed by a water-soluble cobalt(II) complex supported by N,N′-bis(2′-pyridinecarboxamide)-1,2-benzene with high turnover frequency

Abstract

The oxidation and reduction of water is a key challenge in the production of chemical fuels from electricity. Reported here is a soluble cobalt (II) complex, [Co(bpbH2)Cl2] 1 (bpbH2: N,N′-bis(2′-pyridinecarboxamide)-1,2-benzene), a highly active homogeneous electrocatalyst for both electrolytic water oxidation and reduction in purely aqueous solution. Electrochemical studies indicate that the catalyst is a water-soluble molecular species, that is among the most rapid homogeneous catalysts for water oxidation, with a turnover frequency of ∼81.54 s−1 (at pH 8.6, the lowest pH among those of any reported electrocatalysts) at an overpotential of 560 mV. 1 also can catalyze hydrogen evolution from water with a TOF of 376 mol of hydrogen per mole of catalyst per hour at an overpotential of 687.6 mV (pH 7.0). This is attributed to the planar ligand (bpbH2), that coordinates strongly through four nitrogen atoms to the cobalt center, leaving two Cl− ions in axial position and making the Cl− ion ionize in organic solvents or water, and can stabilize both the high and low oxidation states of cobalt well.