Photocatalytic Dinitrogen Reduction to Ammonia over Biomimetic FeMoSx Nanosheets.

Abstract

Reduction of atmospheric dinitrogen (N2) to ammonia (NH3) using water and sunlight in the absence of sacrificial reducing reagents at room temperature is very challenging and is considered an eco-friendly approach to meet the rapidly increasing demand for nitrogen storage, fertilizers, and a sustainable society. Currently, ammonia production via the energy-intensive Haber-Bosch process causes ∼350 million tons of carbon dioxide (CO2) emission per year. Interestingly, natural N2 fixation by the nitrogenase enzyme occurs under ambient conditions. Unfortunately, N2 fixation on biomimetic catalysts has rarely been studied. To mimic biological nitrogen fixation, herein, we synthesized the novel iron molybdenum sulfide (FeMoSx) micro-/nanosheets via a simple hydrothermal approach for the first time. Further, we successfully demonstrated the photochemical conversion of N2 to NH3 over a biomimetic FeMoSx photocatalyst. The estimated yield is around 99.79 ± 6.0 μmol/h/g photocatalyst with a quantum efficiency of ∼0.028% at 532 nm visible-light wavelength. Besides, we also systematically studied the influence of key factors to further improve NH3 yields. Overall, this study paves a new pathway to fabricate carbon-free, photochemical N2 fixation materials for future applications.