Plasmonic silver nanoparticle-deposited n-Bi2S3/p-MnOS diode-type catalyst for enhanced photocatalytic nitrogen fixation: Introducing the defective p-MnOS

Photocatalytic nitrogen reduction reaction (PNRR) is clean and sustainable, considered an ideal synthesis technology for ammonia (NH3). In this study, we in situ developed the n-Bi2S3 nanorod/p-MnOS cubic composite catalyst for the first time using a one-step hydrothermal method, as MnOS, listed in the X-ray diffraction standard data file as an uncharacterized compound, has not been reported since 1965. Then, using a photodeposition technique, Ag nanoparticles (NPs) were added to the surface of the Bi2S3/MnOS to enhance PNRR via the surface plasmon resonance. After different characterization techniques for evaluation, Ag-Bi2S3/MnOS is found to be highly effective in the spatial separation of photogenerated electron-hole pairs due to the charge transfer at the composite interface. Photodeposited Ag is applied as an electron trapper to enhance the spatial separation of charge carriers. Based on their ability to reduce nitrogen under simulated solar light irradiation, the PNRR activities of Bi2S3, MnOS, Bi2S3/MnOS, and 0.5 to 2 % Ag-Bi2S3/MnOS were evaluated. After two hours, the PNRR activity of 1 % Ag-Bi2S3/MnOS produced ammonia 5.9 mmol/g, double the amount of Bi2S3/MnOS composite and approximately 5 times the amounts of Bi2S3 and MnOS materials. PNRR enhancement involves the internal static electron field created at the n-type Bi2S3/p-type MnOS interface and the improved electron conductivity with the photodeposition of Ag NPs, to speed up the reaction of reactive species. The importance of solid solution engineering in material design is demonstrated in this work.