Heteroatom‐Doped Ag<sub>25</sub> Nanoclusters Encapsulated in Metal–Organic Frameworks for Photocatalytic Hydrogen Production
He Wang, Xiyuan Zhang, Wei Zhang, Meng Zhou, Hai‐Long Jiang
Abstract
Abstract Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light‐induced instability and the difficulty of utilizing the photogenerated carriers for photocatalysis pose significant challenges. Here, MAg 24 (M=Ag, Pd, Pt, and Au) NCs doped with diverse single heteroatoms have been encapsulated in a metal–organic framework (MOF), UiO‐66‐NH 2 , affording MAg 24 @UiO‐66‐NH 2 . Strikingly, compared with Ag 25 @UiO‐66‐NH 2 , the MAg 24 @UiO‐66‐NH 2 doped with heteroatom exhibits much enhanced activity in photocatalytic hydrogen production, among which AuAg 24 @UiO‐66‐NH 2 presents the best activity up to 3.6 mmol g −1 h −1 , far superior to all other counterparts. Moreover, they display excellent photocatalytic recyclability and stability. X‐ray photoelectron spectroscopy and ultrafast transient absorption spectroscopy demonstrate that MAg 24 NCs encapsulated into the MOF create a favorable charge transfer pathway, similar to a Z‐scheme heterojunction, when exposed to visible light. This promotes charge separation, along with optimized Ag electronic state, which are responsible for the superior activity in photocatalytic hydrogen production.