Abstract
Ammonia synthesis is vital for global fertilizer production but traditionally relies on the energy-intensive Haber-Bosch process, a major contributor to CO(2) emissions. Photocatalytic nitrogen reduction reaction (PNRR) offers a sustainable alternative by harnessing solar energy under ambient conditions. However, challenges such as low nitrogen adsorption, poor conductivity, and high electron-hole recombination of the photocatalysts limit their efficiency. This study introduces an Fe(3)O(4)@C@ZIF67 core-shell photocatalyst featuring an Fe─N─Co bridged Z-scheme heterojunction. This design incorporates carbon-coated Fe(3)O(4) in ZIF67-D (ZIF67-dodecahedron) with exposed (211) crystalline facets to enhance nitrogen adsorption. Fe─N(4) and Co─N(4) active sites improve catalytic activity, while the carbon layer enhances conductivity and facilitates oxygen vacancy formation. The Fe─N─Co bridged heterojunction further promotes charge separation and transfer. Therefore, the Fe(3)O(4)@C@ZIF67 composite achieves an outstanding ammonia yield of 33.2 mmol L(-1) g(-1) h(-1) (outperforming other systems) with high selectivity and minimal by-products. This work provides valuable insights into the design of high-performance photocatalysts by integrating the advantages of metal-organic frameworks, core-shell architectures, and interfacial engineering, marking a significant step forward in sustainable ammonia synthesis.