Electron Delocalization of Au Nanoclusters Triggered by Fe Single Atoms Boosts Alkaline Overall Water Splitting

The rational design and in-depth understanding of the structure-activity relationship (SAR) of hydrogen and oxygen evolution reaction (HER and OER) bifunctional electrocatalysts are vital to decreasing the energy consumption of hydrogen production by electrochemical water splitting. Herein, we report an inducing electron delocalization method where Fe single atoms as inducers are used to regulate the electron structure of Au nanoclusters by the M-N-C substrate to acquire satisfactory intrinsic HER activity. Meanwhile, Fe single atoms also serve as efficient OER active sites to construct bifunctional electrocatalysts. On account of the strong synergistic effect between Au nanoclusters and Fe single atoms, the hybrid catalyst Au-Fe₁NC/NF performs an outstanding alkaline HER and OER activity. Only 35.6 mV, 246 mV, and 1.52 V are needed to reach 10 mA cm^-2 for alkaline HER, OER, and two-electrode electrolytic cells, respectively. In addition, the bifunctional electrocatalysts also display excellent electrochemical stability. DFT calculations demonstrate that the strong synergistic effect can enhance the O-H bond activation ability of Au nanoclusters and upshift the d-band center of the Fe single atom to promote alkaline electrocatalytic water splitting. The strong synergistic effect is proven to arise from the electron delocalization of Au nanoclusters triggered by Fe single atoms.