Light-Off in Plasmon-Mediated Photocatalysis

In this paper, we study photothermal rate enhancement in plasmon-mediated photocatalysis using the example of CO oxidation over nanofabricated neat Pd and Au₅₀Pd₅₀ alloy catalysts. We find that rate enhancement differs by orders of magnitude depending on the position of catalyst operation along the light-off curve measured in the dark, indicating that small fluctuations in reactor temperature or temperature gradients across a sample may have a significant impact on the global and local photothermal rate enhancement.

We use first-principles informed microkinetic modelling to qualitatively rationalize the distinct conversion profiles observed for the two catalyst materials in terms of the influence of the underlying energetics on the kinetics.

Figure credit: Tiburski, Boje, et al., ACS Nano 2021 (ASAP). doi: 10.1021/acsnano.1c01537.