Synergistic effect of bimetallic active sites on Ce doped NH2–MIL-125 for promoting photocatalytic conversion of nitrogen to NH3

Abstract

Ammonia (NH3), one of the most abundant inorganic compounds in the world, is highly demanded in the international market. NH3 is mainly synthesized using Haber-Bosch technology, which severely pollutes the environment and consumes high quantities of energy. In this study, a series of Ce doped NH2–MIL-125 (Ce–NH2–MIL-125) was prepared using a one-step solvothermal method to assess the activity of photocatalytic nitrogen fixation. The applied light energy interval of Ce–NH2–MIL-125 was widened, and the establishment of a Ce–O–Ti chemical bond optimized the transport path of the photogenerated carriers. This excellent photoelectric performance represents a significant improvement in the separation capacity of the photogenerated electrons and holes in Ce–NH2–MIL-125. Doping with Ce resulted in the generation of dual active sites, Ti4+/Ti3+ and Ce4+/Ce3+, in NH2–MIL-125; additionally, the increase in the amount of Ti3+ was significantly higher than that of the initial NH2–MIL-125. The synergistic effect of the bimetallic active sites in Ce–NH2–MIL-125 accelerated the photocatalytic nitrogen fixation reaction. Under full spectrum radiation, the ammonia generation rate of NH2–MIL-125 was 10.6 µmol g−1 h−1. Ce–NH2–MIL-125–1.0 exhibited the highest capacity for nitrogen fixation; the highest ammonia formation rate was 39.4 µmol g−1 h−1. The photocatalytic activity of Ce–NH2–MIL-125–1.0 was 3.7 times higher than that of NH2–MIL-125. This study provides a reference for catalytic research on modified NH2–MIL-125.