Nitrogenase-mimic iron-containing chalcogels for photochemical reduction of dinitrogen to ammonia

Abstract

Significance: In nature, nitrogenase fixes nitrogen into biologically usable forms under ambient conditions. Today, half of the world’s nitrogen fixation is achieved through the industrial Haber–Bosch process, which operates at elevated temperature and pressure. Here, we present a synthetic nitrogenase mimic in the form of chalcogel composed of molybdenum and iron-containing biomimetic clusters that can accomplish photocatalytic N 2 fixation and conversion to NH 3 at ambient temperature and pressure. Surprisingly, the iron–sulfur chalcogels without molybdenum are observed to have a higher activity toward N 2 reduction. The results reported here will greatly expand the scope of materials design and engineering for the creation of highly active iron-based N 2 reduction catalysts operating in mild conditions.