2D Plasmonic Photocatalyst Enables Highly Efficient Hot-Electron-Mediated Surface Reactions under Red Light Irradiation.

Gan, Yaxi; Kalantari Osgouei, Ataollah; Ahrens, Alexander; Wang, Bofang; Zhou, Jingyi; Zhan, Jun-Zheng; Zeng, Dan; Nie, Shengqiang et al. · ACS Nano · 2025

basic_science · Level V

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Abstract

Plasmonic photocatalysis is promising for solar-driven chemical transformations under mild conditions; however, conventional materials like aluminum, copper, silver, and gold are resonant at short wavelengths, limiting their use in the red to near-infrared sunlight spectrum. In this study, we have developed a class of antenna-reactor (AR) photocatalyst based on two-dimensional (2D) plasmonic materials, Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub>, also known as MXenes. A Ru-loaded Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> plasmonic photocatalyst achieves a turnover frequency of approximately 2 s<sup>-1</sup> and energy efficiency of 10% for hydrogen production under 660 nm light excitation, being 2-3 orders of magnitude superior to the performance achieved in thermocatalysis. This 2D plasmonic antenna demonstrates superiority over the benchmark CuRu surface-alloy AR structure in hot-electron-driven processes under red light excitation. Kinetic studies suggest that the rate-determining step in both photo- and thermocatalysis is nitrogen's associative desorption. Hot electrons enhance activity by promoting the removal of adsorbed nitrogenous species.