Eppur Si Riscalda - and yet, It (Just) Heats Up: Further Comments on “Quantifying Hot Carrier and Thermal Contributions in Plasmonic Photocatalysis”

Our Comment [1] on recent attempts to distinguish thermal and non-thermal (``hot carrier'') contributions to plasmon-assisted photocatalysis [2] initiated a re-evaluation process of previous literature on the topic within the nano-plasmonics and chemistry communities. The Response of Zhou et al [3] attempts to defend the claims of the original paper [2].

In this manuscript, we show that the Response [3] presents additional data that further validates our central criticism: inaccurately measured temperatures (that are lower than the actual temperature of the catalyst) led Zhou \etal to incorrectly claim conclusive evidence of non-thermal effects. We identify flaws in the experimental setup (e.g. the use of the default settings for the thermal camera and incorrect positioning of the thermometer) that may have led Zhou et al to make such claims. We further show that the Response contains several factual errors and does not address the technical problems we identified with the data acquisition in [2]. We demonstrate that both the Response [3] and the original paper [2] contain additional faults, for example, in the power determination and in the normalization of the rate to the catalyst volume, and exhibit misconceptions regarding the thermo-optic response of metal nanostructures. The burden of proof required by the proposal of a novel physical mechanism has simply not been met, especially when the existing data can be modeled exquisitely by conventional theory.
[1] Y. Sivan, J. Baraban, I. W. Un & Y. Dubi, Science Vol. 364, Issue 6439, eaaw9367. https://science.sciencemag.org/content/364/6439/eaaw9367.abstract