Plasmonic Enhanced Reactive Oxygen Species Activation on Low-Work-Function Tungsten Nitride for Direct Near-Infrared Driven Photocatalysis.

Realizing near-infrared (NIR) driven photocatalytic reaction is one of the promising strategies to promote the solar energy utilization and photocatalytic efficiencies. However, effective reactive oxygen species (ROS) activation under NIR irradiation remains to be great challenge for nearly all previously reported photocatalysts. Herein, the cubic-phase tungsten nitride (WN) with strong plasmonic NIR absorption and low-work function (≈3.59 eV) is proved to be able to mediate direct ROS activation by both of experimental observation and theoretical simulation. The cubic WN nanocubes (NCs) are synthesized via the hydrothermal-ammonia nitridation process and its NIR-driven photocatalytic properties, including photocatalytic degradation, hydroxylation, and de-esterification, are reported for the first time in this work. The 3D finite element simulation results demonstrate the size dependent and wavelength tuned plasmonic NIR absorption of the WN NCs. The NIR-driven photocatalytic mechanism of WN NCs is proposed based on density functional theory (DFT) calculated electronic structure and facet dependent O (or H O) molecular activation, radicals scavenging test, spin trapped electron paramagnetic resonance measurements, and ultraviolet photoelectronic spectrum (UPS). Overall, the results in this work pave a way for the application of low-work-function materials as highly reactive NIR photocatalyst.