Bio-Inspired Ni Dinuclear Complexes As Heterogeneous Catalysts For Hydrogen Evolution

A major challenge in the sustainable production of hydrogen is lowering the electrochemical overpotential and the activation energy of the hydrogen evolution reaction. Some enzymes have two metallic Ni centers and catalyze this reaction with high activity. Taking inspiration from them, we have developed two novel dinuclear Ni(II) complexes, Ni-PATIO and Ni-PACO, with promise as molecular catalysts. Ni-PACO exhibits a square-planar geometry for both Ni(II) and two-fold rotational symmetry both in solid and solution states, whereas Ni-PATIO displays one square-planar Ni(II) center and one octahedral Ni(II) configuration, which confer it magnetic properties. We show that both complexes can be immobilized on common glassy carbon electrodes without any additives and produce hydrogen from water at significantly reduced potentials.