Defects Calculation and Accelerated Interfacial Charge Transfer in a Photoactive MOF‐Based Heterojunction

Abstract Photocatalytic hydrogen production is currently considered a clean and sustainable route to meet the energy and environmental issues. Among, heterojunction photocatalysts have been developed to improve their photocatalytic efficiency. Defect engineering of heterojunction photocatalysts is attractive due to it can perform as electron trap and change the band structure to optimize the interfacial separation rate of photogenerated electron–hole pairs. Here, the MOF‐based heterojunction photocatalysts with theoretically high reduction and oxidation abilities are successfully synthesized, denoted ZrO ₂ /Pt/Zr‐MOF‐ X , with tuned linker defectivity through an in situ electrochemical route. The defectivity are rationally calculated from the TG and ¹ H NMR results. A positive correlation is found between the defectivity and photocatalytic activity, and ZrO ₂ /Pt/Zr‐MOF‐6 with the optimized defectivity of ca. 35% exhibits the highest hydrogen production rate of up to 2923 µmol g ⁻¹ h ⁻¹ , illustrating the importance of structural defects in heterojunction photocatalysts. Ultrafast transient absorption spectroscopy and electron spin resonance results unveil the highest carrier concentration and charge separation efficiency in the defected heterostructure of ZrO ₂ /Pt/Zr‐MOF‐6 through a direct Z‐scheme contact, leading to its efficient photocatalysis through the high redox power.