Designing a Redox Heterojunction for Photocatalytic “Overall Nitrogen Fixation” under Mild Conditions

Ammonia and nitrates are the most fundamental and significant raw ingredients in human society. Till now, industrial synthetic ammonia by Haber-Bosch process and industrial synthetic nitrates by the Ostwald process have encountered increasingly serious challenges, i.e., high energy consumption, high cost, and environment-harmful gas emissions. Therefore, developing alternative approaches to achieve nitrogen fixation to overcome the inherent deficiencies of the well-established Haber-Bosch and Ostwald processes has fascinated scientists for many years, especially the simultaneous formation of ammonia and nitrate directly from N₂ molecules, which has been rarely studied. Herein, a heterojunction-based photocatalytic system is designed to successfully achieve "overall nitrogen fixation," a sustainable and simultaneous conversion of N₂ molecules into ammonia and nitrate products under mild conditions. In this heterojunction, interfacial charge redistribution (ICR) promotes selective accumulations of photogenerated electrons and holes in the CdS and WO₃ components. As a result, N₂ molecules can be activated and reduced to ammonia products with yields of 35.8 µmol h^-1 g^-1 by a multi-electron process, and synchronously oxidized into nitrate products with yields of 14.2 µmol h^-1 g^-1 by a hole-induced oxidation coupling process. This work provides a novel insight and promising approach to realize artificial nitrogen fixation under mild condition.