Plasmon-enabled N2 photofixation on partially reduced Ti3C2 MXene

Abstract

Benefiting from the superior conductivity, rich surface chemistry and tunable bandgap, Ti₃C₂ MXene has become a frontier cocatalyst material for boosting the efficiency of semiconductor photocatalysts. It has been theoretically predicted to be an ideal material for N₂ fixation. However, the realization of N₂ photofixation with Ti₃C₂ as a host photocatalyst has so far remained experimentally challenging. Herein, we report on a sandwich-like plasmon- and an MXene-based photocatalyst made of Au nanospheres and layered Ti₃C₂, and demonstrate its efficient N₂ photofixation in pure water under ambient conditions. The abundant low-valence Ti (Ti^(4−x)+) sites in partially reduced Ti₃C₂ (r-Ti₃C₂) produced by surface engineering through H₂ thermal reduction effectively capture and activate N₂, while Au nanospheres offer plasmonic hot electrons to reduce the activated N₂ into NH₃. The Ti^(4−x)+ active sites and plasmon-generated hot electrons work in tandem to endow r-Ti₃C₂/Au with remarkably enhanced N₂ photofixation activity. Importantly, r-Ti₃C₂/Au exhibits ultrahigh selectivity without the occurrence of competing H₂ evolution. This work opens up a promising route for the rational design of efficient MXene-based photocatalysts.