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