An intramolecular cobalt-peptoid complex as an efficient electrocatalyst for water oxidation at low overpotential

Water electrolysis is the simplest way to produce hydrogen, as a clean renewable fuel. However, the high overpotential and slow kinetics hamper its applicability. Designing efficient and stable electrocatalysts for water oxidation (WO), which is the first and limiting step of the water splitting process, can overcome this limitation. However, the development of such catalysts based on non-precious metal ions is still challenging. Herein we describe a bio-inspired Co(iii)-based complex i.e., a stable and efficient molecular electrocatalyst for WO, constructed from a peptidomimetic oligomer called peptoid - N-substituted glycine oligomer - bearing two binding ligands, terpyridine and bipyridine, and one ethanolic group as a proton shuttler. Upon binding of a cobalt ion, this peptoid forms an intramolecular Co(iii) complex, that acts as an efficient electrocatalyst for homogeneous WO in aqueous phosphate buffer at pH 7 with a high faradaic efficiency of up to 92% at an overpotential of about 430 mV, which is the lowest reported for Co-based homogeneous WO electrocatalysts to date. We demonstrated the high stability of the complex during electrocatalytic WO and that the ethanolic side chain plays a key role in the stability and activity of the complex and also in facilitating water binding, thus mimicking an enzymatic second coordination sphere.