Ammonia Synthesis with Visible Light and Quantum Dots.

Light-assisted synthesis of ammonia from nitrate and nitrite sources is a sustainable approach to reduce the burden of the energy-intensive Haber-Bosch process. However, poor selectivity and the need for UV-active photocatalysts are the current bottlenecks in the synthesis of ammonia from nitrate and nitrite sources. Herein, we introduce selective visible-light-driven ammonia production from nitrate and nitrite ions with indium phosphide quantum dots (InP QDs) as the photocatalyst. The presence of catalytic indium sites and microenvironment modulation through an interplay of catalyst-reactant interactions resulted in efficient and selective ammonia formation under visible light. Ammonia was produced in an attractive yield of ∼94% in both aqueous and gaseous phases within 2 h of visible-light irradiation at room temperature. A decent formation of ammonia was observed under sunlight as well, strengthening the translational prospects of InP QD photocatalysts. Mechanistic investigations ascertained a negligible role of competing hydrogen evolution in direct nitrate reduction, confirming the active participation of photoexcited charge carriers from InP QDs in the ammonia synthesis. Kinetic studies revealed the energetically challenging nitrate-to-nitrite conversion as the rate-determining step, with subsequent reactions proceeding with ∼100% conversion to yield ammonia. A series of experiments concluded that water is the proton source in the InP QD-photocatalyzed synthesis of ammonia. Our study shows the impact of the rationally designed core and surface of InP QD-based photocatalysts in developing sustainable routes to produce ammonia beyond the Haber-Bosch process.