Boosting N[tbnd]N tri-bond activation and NH3 generation rate through simple surface Ag modification

Abstract

NH3 photosynthesis from nitrogen remains a big challenge due to the extreme difficulty for the activation of NN bond. In this work, Ag-modified MoO3·0.55 H2O nanorods (named as Ag@Mo) are prepared by a simple photoreduction method. Under visible light (λ ≥ 420 nm) for 60 min, the NH3 yield over 2%Ag@Mo (molar ratio of Ag to MoO3·0.55 H2O) reaches 242.0 μmol·gcat−1, which is about 2.8 times higher than MoO3·0.55 H2O under the same conditions. The effect of Ag modification on photocatalytic ammonia synthesis is explored through experiments and theoretical calculations. The excellent photocatalytic performance is mainly attributed to the localized surface plasmon resonance effect of Ag and the successful construction of Mott-Schottky junction, which improves light utilization efficiency and reduces carrier recombination efficiency, respectively. Moreover, density functional theory calculations theoretically prove that over Ag@Mo, Ag provides new adsorption sites, and the NN tri-bond length is elongated by about 16.2%, confirming that Ag modification obviously promotes the activation of NN tri-bond. The ammonia generation rate is obviously higher than the previously reported results.