Antimony-Doped Wide Bandgap Molybdenum Trioxide with Enhanced Localized Surface Plasmon Resonance for Nitrogen Photofixation.

Plasmonic metal oxides are promising photocatalysts for the artificial photosynthesis of green ammonia due to localized surface plasmon resonance (LSPR) enhanced photoconversion and rich surface oxygen vacancies improved chemisorption and activation of dinitrogen molecules. However, these oxygen vacancies are unstable during the photocatalytic process and could be oxidized by photogenerated holes, leading to the vanishing of the LSPR. Here, we fabricated antimony-doped molybdenum trioxide nanosheets with stable plasmonic absorption extending into the near-infrared (NIR) range, even after harsh treatment in oxidative atmospheric conditions at high temperatures. For undoped plasmonic MoO3-x nanosheets, the LSPR originates from the abundant oxygen vacancies that vanish after heat treatment at high temperatures in air, leading to the disappearance of the LSPR absorption. Sb doping does not significantly increase the concentration of oxygen vacancies while donating more free electrons because Sb can keep a lower oxidation state. Heat treatment diminished the oxygen vacancies while not affecting the low oxidation state of Sb. As a result, heat-treated Sb-doped MoO3-x nanosheets still show strong LSPR absorption in the NIR range. Both experimental results and theoretical calculations demonstrated that add-on states close to the Fermi level are formed due to the Sb doping and high concentration of oxygen vacancies. The prepared samples were used for photocatalytic nitrogen reduction and showed an LSPR-dependent photocatalytic performance. The present work has provided an effective strategy to stabilize the LSPR of plasmonic semiconductor photocatalysts.