Numerous atomically precise coinage metal nanoclusters have been synthesized, exhibiting diverse structures and promising properties for catalytic and other functional applications. However, silver nanoclusters featuring layered core structures remain largely unexplored, limiting investigations into the effects of atomic arrangements on catalytic functions. Herein, we report the synthesis and atomic level structure of a novel thiolate-phosphine co-stabilized silver nanocluster, Ag₂₆(SR)₁₆(DPPE)₄Cl₂ (denoted as Ag₂₆), where SR is 3,5-bis(trifluoromethyl)benzenethiolate and DPPE is 1,2-bis(diphenylphosphino)ethane. Single-crystal X-ray diffraction analysis reveals that Ag₂₆ comprises a three-layered Ag₁₈ core, with each layer consisting of six silver atoms arranged in a distorted parallelogram configuration. This Ag₁₈ core is stabilized by four Ag₂(SR)₄(DPPE) metal-ligand motifs and two chlorides. Notably, TiO₂-supported Ag₂₆ nanoclusters (Ag₂₆/TiO₂) demonstrated promising photocatalytic performance for solar-driven hydrogen production, achieving a hydrogen evolution rate of 2006 μmol·g⁻¹·h⁻¹, representing 16.2- and 6.5-fold enhancements compared to bare TiO₂ support and similarly sized Ag₂₅/TiO₂ nanoclusters, respectively. The layered atomic arrangement in the Ag₂₆ core favorably regulates the energy level alignment with TiO₂, leading to efficient photogenerated charge separation and enhanced catalytic activity. This work highlights the potential of structurally tailored silver nanoclusters and offers valuable insights for the design of advanced materials for energy conversion applications.

Photocatalysis presents a promising pathway for clean energy generation by leveraging solar energy under environmentally benign conditions with minimal pollutant emissions. However, its widespread application is hindered by low catalytic efficiency, stemming from limited light absorption, rapid recombination of photo-excited electrons, and suboptimal charge carrier potential for target reactions. This review discusses advanced strategies to enhance photocatalytic performance by modulating photocatalytic supports and refining co-catalysts. Techniques such as hydrogenation and extrinsic doping of photocatalytic supports are highlighted for their ability to broaden light absorption and prolong electron lifetimes. Additionally, the strategic design of co-catalysts, including the use of nanoclusters and atomically dispersed catalysts, is emphasized for optimizing charge carrier potential and improving atomic utilization efficiency. This review aims to guide researchers in developing high-performance photocatalysts for clean energy applications, including CO₂ reduction and plastic waste photoreforming, thereby contributing to the advancement of sustainable energy technologies.