LAUSR

The construction of strong metal–support interactions (SMSI) is an effective strategy to enhance and control heterogeneous catalysts. However, conventional methods require pre‐synthesized metal‐loaded catalysts, followed by SMSI formation via high‐temperature treatment under oxidative/reductive atmospheres, adsorbate‐mediated treatment, and photo‐treatment, adding complexity to catalyst synthesis and hindering continuous interfacial tuning. In this work, a “photobreeding” method is employed to treat Zn0.8Cd0.2S, leveraging the UV‐induced photochromic reaction of ZnS to generate metallic Zn at room temperature, while CdS remains inert. Zn0.8Cd0.2S‐derived CdS directly encapsulates the generated Zn, enabling direct synthesis of SMSI catalysts without additional treatments. Furthermore, the interfacial properties can be continuously tuned by adjusting the photobreeding duration. The catalytic performance of SMSI catalysts synthesized via photobreeding exhibits a 3.1‐fold enhancement over the initial catalysts. To further boost performance, viologen, an electron mediator, is introduced to form a surface charge transfer complex. The resulting ZCS‐SMSI‐120/PV exhibits a hydrogen evolution rate of 48.7 mmol·g−1·h−1 without the use of noble metals, representing one of the highest values reported to date. This direct SMSI synthesis approach holds promise for applications in H2 production, CO2 reduction, biomass conversion, organic synthesis, and so on.