Treasure-bowl style bifunctional site in cerium-tungsten hetero-clusters for superior solar-driven hydrogen production.

Electrochemical water splitting powered by renewable energy sources hold potential for clean hydrogen production. However, there is still persistent challenges such as low solar-to-hydrogen conversion efficiency and sluggish oxygen evolution reactions. Here, we address the poor kinetics by studying and strengthening the coupling between Ce and W, and concurrently establishing Ce-W bi-atomic clusters on P,N-doped carbon (WN/WC-CeO 2- x @PNC) with a "treasure-bowl" style. The bifunctional active sites are established using a novel and effective self-sacrificial strategy involving in situ induced defect formation. In addition, by altering the coupling of the W(d)-N(p) and W(d)-Ce(f) orbitals in the WN/WC-CeO 2- x supramolecular clusters, we are able to disrupt the linear relationship between the binding energies of reaction intermediates, a key to obtain high catalytic performance for transition metals. Through the confinement of the WN/WC-CeO 2- x composite hetero-clusters within the sub-nanometre spaces of hollow nano-bowl-shaped carbon reactors, a stable and efficient hydrogen production via water electrolysis could be achieved. When assembled together with a solar GaAs triple junction solar cell, a solar-to-hydrogen conversion efficiency of 18.92% in alkaline media could be realized. We show that the key to establish noble metal free catalysts with high efficiency lies in the fine-tuning of the metal-metal interface, forming regions with near optimal adsorption energies for the reaction intermediates participating in water electrolysis.