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In a recent paper~[Nature Catalysis 3, 573 (2020)], Robatjazi {\em et al.}demonstrate hydrodefluorination on Al nanocrystals decorated by Pd islandsunder illumination and under external heating. They conclude thatphotocatalysis accomplishes the desired transformation \ce{CH3F + D2 -> CH3D +DF} efficiently and selectively due to "hot" electrons, as evidenced by anillumination-induced reduction of the activation energy.  Although some of the problems identified in prior work by the same group havebeen addressed, scrutiny of the data in~[Nature Catalysis 3, 573 (2020)] raisesdoubts about both the methodology and the central conclusions. First, we showthat the thermal control experiments in~[Nature Catalysis 3, 573 (2020)] do notseparate thermal from "hot electron" contributions, and therefore anyconclusions drawn from these experiments are invalid. We then show that animproved thermal control implies that the activation energy of the reactiondoes not change, and that an independent purely thermal calculation (basedsolely on the sample parameters provided in the original manuscript) explainsthe measured data perfectly. For the sake of completeness, we also addresstechnical problems in the calibration of the thermal camera, an unjustifiabledisqualification of some of the measured data, as well as concerning aspects ofthe rest of the main results, including the mass spectrometry approach used toinvestigate the selectivity of the reaction, and claims about the stoichiometryand reaction order. All this shows that the burden of proof for involvement ofhot electrons has not been met.

Matters Arising in -- "Plasmon-driven carbon-fluorine (C(sp^$3$)-F) bond activation with mechanistic insights into hot-carrier-mediated pathways"