Correlating Heteroatoms Doping, Electronic Structures, and Photocatalytic Activities of Single‐Atom‐Doped Ag<sub>25</sub>(SR)<sub>18</sub> Nanoclusters
Ye Liu, Deng Long, Andreas Springer, Rongbin Wang, Norbert Koch, Matthias Schwalbe, Nicola Pinna, Yu Wang
Abstract
Atomic‐level manipulation of catalysts is important for both fundamental studies and practical applications. Here, the central metal atom in an atomically precise Ag 25 nanocluster (NC) is replaced with a single Pd, Pt, and Au atom, respectively, and employed as a model system to study the structure–property–activity relationship at the atomic level. While the geometric structures are well‐preserved after doping, the electronic structures of Ag 25 NCs are significantly altered. The combination of Ag 25 and TiO 2 enhances the charge separation at the interface, exhibiting a 10 times higher hydrogen production rate in photocatalytic hydrogen evolution reaction compared to bare TiO 2 . Further results show that heteroatoms doping has a negative impact on performance, particularly in the cases of Pd and Au doping. Ultraviolet photoelectron spectroscopy measurements and density functional theory calculations suggest that the lower activities are due to an energy mismatch between the levels of doped NCs and TiO 2 . These findings not only reveal the impact of heteroatoms doping on the electronic properties and photocatalytic activities of NCs, but can also guide the design of heterometallic NCs for photocatalytic applications.