Integrating electronic structure regulation and dynamic active sites construction on NixCd1-xS-Ni0 photocatalyst for efficient hydrogen evolution.

ABSTRACT

Regulating electronic structure and enriching active sites of photocatalysts are effective strategies to promote hydrogen evolution. Herein, a unique NixCd1-xS-Ni0 photocatalyst, including the surface nickel (Ni) doping and atomic Ni0 anchoring sites, is successfully prepared by Ni2+ ions exchange reaction (Ni2++ CdS â†’ NixCd1-xS) and in-situ photo-induction of Ni0(Ni2++NixCd1-xS→hνNixCd1-xS-Ni0), respectively. As to Ni doping, the Ni replaced cadmium (Cd) atoms introduce hybridized states around the Fermi level, modulating the electronic structure of adjacent S atoms and optimizing the photocatalytic activity of sulfur (S) atoms. Besides, photogenerated Ni0 atoms, anchored on unsaturated S atoms, act as charge transfer bridges to reduce Ni2+ ions in the solution to Ni clusters (NixCd1-xS-Ni0→ne-NixCd1-xS-Ni). Subsequently, the displacement reaction of Ni clusters with protons (H+) spontaneously proceeds to produce hydrogen (H2) in an acidic solution (NixCd1-xS-Ni→2H+H2↑+Ni2++NixCd1-xS-Ni0). The equilibrium of photo-deposition/dissolution of Ni clusters realizes the construction of dynamic active sites, providing sustainable reaction centers and enhancing surface redox kinetics. The NixCd1-xS-Ni0 exhibits a high hydrogen evolution rate of 428 mmol·h-1·g-1 with a quantum efficiency of 75.6 % at 420 nm. This work provides the optimal S electronic structure for photocatalytic H2 evolution and constructs dynamic Ni clusters for chemical replacement reaction. This work provides the optimal S electronic structure for photocatalytic H2 evolution and constructs dynamic Ni clusters for displacement reaction, opening a dual pathway for efficient water reduction.