A Cobalt@Cucurbit[5]uril Complex as a Highly Efficient Supramolecular Catalyst for Electrochemical and Photoelectrochemical Water Splitting.

A host-guest complex self-assembled through Co2+ and cucurbit[5]uril (Co@CB[5]) is used as a supramolecular catalyst on the surface of metal oxides including porous indium tin oxide (ITO) and porous BiVO4 for efficient electrochemical and photoelectrochemical water oxidation. When immobilized on ITO, Co@CB[5] exhibited a turnover frequency (TOF) of 9.9 s-1 at overpotential η=550 mV in a pH 9.2 borate buffer. Meanwhile, when Co@CB[5] complex was immobilized onto the surface of BiVO4 semiconductor, the assembled Co@CB[5]/BiVO4 photoanode exhibited a low onset potential of 0.15 V (vs. RHE) and a high photocurrent of 4.8 mA cm-2 at 1.23 V (vs. RHE) under 100 mW cm-2 (AM 1.5) light illumination. Kinetic studies confirmed that Co@CB[5] acts as a supramolecular water oxidation catalyst, and can effectively accelerate interfacial charge transfer between BiVO4 and electrolyte. Surface charge recombination of BiVO4 can be also significantly suppressed by Co@CB[5].