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Reply to: Distinguishing thermal from non-thermal contributions to plasmonic hydrodefluorination

Nature Catalysis volume 5, pages 247–250 (2022)Cite this article

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The Original Article was published on 28 March 2022

replying to Y. Dubi et al. Nature Catalysis https://doi.org/10.1038/s41929-022-00767-6 (2022).

Dubi et al.1 have stated that there is an issue in our recent plasmonic hydrodefluorination (HDF) work2 with the measurement of the reaction selectivity and that a simple thermal theory can explain our discussion of the non-thermal hot-carrier contribution to the reaction pathway. Unfortunately, their thermal argument is based on problematic models and invalid emissivity arguments that we have previously proven to be incorrect3. We further elaborate on that here. Specifically, the analysis of Dubi et al. is based on an entirely different set of premises. Interestingly, their model reproduces their own incorrectly inferred reaction rates. We also validate our mass spectroscopy analysis and, in addition, provide detailed photothermal simulations that further corroborate the accuracy of our thermal camera for surface temperature measurements of the catalyst and support our discussion of hot-carrier contributions to the observed illumination-induced catalytic reactivity. Finally, we discuss the light-induced changes to the reaction orders compared with thermal control experiments. Our response provides additional evidence for hot-carrier-induced chemistry and shows that the measured results cannot be explained by thermal models.

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Fig. 1: Photothermal simulations for hydrodefluorination of CH3F on Al-Pd photocatalysts.
Fig. 2: Mass spectroscopy analysis.

Data availability

All data are available from the corresponding authors upon reasonable request.

References

  1. Dubi, Y., Ieng, W. U., Baraban, J. H. & Sivan, Y. Distinguishing thermal from non-thermal contributions to plasmonic hydrodefluorination. Nat. Catal. https://doi.org/10.1038/s41929-022-00767-6 (2022).

  2. Robatjazi, H. et al. Plasmon-driven carbon–fluorine (C(sp3)–F) bond activation with mechanistic insights into hot-carrier-mediated pathways. Nat. Catal. 3, 564–573 (2020).

    Article  CAS  Google Scholar 

  3. Zhou, L. et al. Response to comment on ‘Quantifying hot carrier and thermal contributions in plasmonic photocatalysis’. Science 364, eaaw9545 (2019).

    Article  CAS  Google Scholar 

  4. Swearer, D. F. et al. Plasmonic photocatalysis of nitrous oxide into N2 and O2 using aluminum-iridium antenna-reactor nanoparticles. ACS Nano 13, 8076–8086 (2019).

    Article  CAS  Google Scholar 

  5. Kim, K. H., Watanabe, K., Mulugeta, D., Freund, H.-J. & Menzel, D. Enhanced photoinduced desorption from metal nanoparticles by photoexcitation of confined hot electrons using femtosecond laser pulses. Phys. Rev. Lett. 107, 47401 (2011).

    Article  Google Scholar 

  6. Watanabe, K., Menzel, D., Nilius, N. & Freund, H.-J. Photochemistry on metal nanoparticles. Chem. Rev. 106, 4301–4320 (2006).

    Article  CAS  Google Scholar 

  7. Mubeen, S. et al. An autonomous photosynthetic device in which all charge carriers derive from surface plasmons. Nat. Nanotechnol. 8, 247–251 (2013).

    Article  CAS  Google Scholar 

  8. Zhou, L. et al. Quantifying hot carrier and thermal contributions in plasmonic photocatalysis. Science 362, 69–72 (2018).

    Article  CAS  Google Scholar 

  9. Marimuthu, A., Zhang, J. & Linic, S. Tuning selectivity in propylene epoxidation by plasmon mediated photo-switching of Cu oxidation state. Science 339, 1590–1593 (2013).

    Article  CAS  Google Scholar 

  10. Robatjazi, H. et al. Plasmon-induced selective carbon dioxide conversion on Earth-abundant aluminum-cuprous oxide antenna-reactor nanoparticles. Nat. Commun. 8, 27 (2017).

    Article  Google Scholar 

  11. Qi, J. et al. Dynamic control of elementary step energetics via pulsed illumination enhances photocatalysis on metal nanoparticles. ACS Energy Lett. 5, 3518–3525 (2020).

    Article  CAS  Google Scholar 

  12. Zhou, L. et al. Light-driven methane dry reforming with single atomic site antenna-reactor plasmonic photocatalysts. Nat. Energy 5, 61–70 (2020).

    Article  CAS  Google Scholar 

  13. Kale, M. J., Avanesian, T., Xin, H., Yan, J. & Christopher, P. Controlling catalytic selectivity on metal nanoparticles by direct photoexcitation of adsorbate-metal bonds. Nano Lett. 14, 5405–5412 (2014).

    Article  CAS  Google Scholar 

  14. Jain, P. K. Comment on ‘Thermal effects—an alternative mechanism for plasmon-assisted photocatalysis’ by Y. Dubi, I. W. Un and Y. Sivan, Chem. Sci., 2020, 11, 5017. Chem. Sci. 11, 9022–9023 (2020).

    Article  CAS  Google Scholar 

  15. Dubi, Y., Un, I. W. & Sivan, Y. Reply to the ‘Comment on ‘Thermal effects—an alternative mechanism for plasmon-assisted photocatalysis’. Chem. Sci. 11, 9024–9025 (2020).

    Article  CAS  Google Scholar 

  16. Li, H., Rivallan, M., Thibault-Starzyk, F., Travert, A. & Meunier, F. C. Effective bulk and surface temperatures of the catalyst bed of FT-IR cells used for in situ and operando studies. Phys. Chem. Chem. Phys. 15, 7321–7327 (2013).

    Article  CAS  Google Scholar 

  17. Abuseada, M., Wei, C., Spearrin, R. M. & Fisher, T. S. Solar-thermal production of graphitic carbon and hydrogen via methane decomposition. Energy Fuels https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.1c04405 (2022).

  18. Baffou, G. et al. Photoinduced heating of nanoparticle arrays. ACS Nano 7, 6478–6488 (2013).

    Article  CAS  Google Scholar 

  19. Madey, T. E., Yates, J. T., King, D. A. & Uhlaner, C. J. Isotope effect in electron stimulated desorption: oxygen chemisorbed on tungsten. J. Chem. Phys. 52, 5215–5220 (1970).

    Article  CAS  Google Scholar 

  20. NIST Mass Spectrometry Data Center in NIST Chemistry WebBook, NIST Standard Reference Database Number 69 (eds Linstrom, P. J. & Mallard, W. G.) NIST MS number 41 (NIST, 2022); https://webbook.nist.gov/cgi/inchi?ID=C593533&Mask=200

  21. Spata, V. A. & Carter, E. A. Mechanistic insights into photocatalyzed hydrogen desorption from palladium surfaces assisted by localized surface plasmon resonances. ACS Nano 12, 3512–3522 (2018).

    Article  CAS  Google Scholar 

  22. Sytwu, K. et al. Driving energetically unfavorable dehydrogenation dynamics with plasmonics. Science 371, 280–283 (2021).

    Article  CAS  Google Scholar 

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Author information

Author notes

  1. Emily A. Carter

    Present address: Department of Mechanical and Aerospace Engineering and the Andlinger Center for Energy and the Environment, Princeton University, Princeton, NJ, USA

  2. These authors contributed equally: Hossein Robatjazi, Andrea Schirato.

Authors and Affiliations

  1. Department of Chemistry, Rice University, Houston, TX, USA

    Hossein Robatjazi, Peter Nordlander & Naomi J. Halas

  2. Department of Physics, Politecnico di Milano, Milan, Italy

    Andrea Schirato

  3. Italian Institute of Technology, Genoa, Italy

    Andrea Schirato

  4. Department of Electrical and Computer Engineering, Rice University, Houston, TX, USA

    Alessandro Alabastri & Naomi J. Halas

  5. Department of Chemical Engineering, University of California, Santa Barbara, Santa Barbara, CA, USA

    Phillip Christopher

  6. Office of the Chancellor and Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, CA, USA

    Emily A. Carter

  7. Department of Physics and Astronomy, Rice University, Houston, TX, USA

    Peter Nordlander & Naomi J. Halas

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  1. Hossein Robatjazi
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Contributions

H.R. and A.S. prepared the draft of the manuscript. A.S. and A.A. carried out the photothermal calculations. H.R., A.S., A.A., P.C., E.A.C., P.N. and N.J.H. discussed the results and contributed to the final manuscript preparation.

Corresponding authors

Correspondence to Hossein Robatjazi or Naomi J. Halas.

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Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Catalysis thanks Jacinto Sa and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Electron impact ionization mass spectrum of CH3F.

There is no interference between the spectrum and CH3D tracing at m/z 17 or other species in the m/z 16-30 range. The lack of interference and our near-perfect carbon mass balance confirm that there is no need for a full mass range scan to search for possible unknown species, as such species were either not present or did not interfere with mass traces associated with reactants and the primary product. The authors of ref. 1 referred to the same database when raising their self-contradictory argument. We carefully consider EI fragmentation in our studies and select mass traces with minimum overlap (when possible). If present, EI interferences are readily addressable using the expected reaction rates and overlap percentages (available from the literature). Figure adapted with permission from ref. 20, NIST Mass Spectrometry Data Center.

Supplementary information

Supplementary Information

Supplementary Notes 1–5, Figs. 1 and 2, and references.

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Robatjazi, H., Schirato, A., Alabastri, A. et al. Reply to: Distinguishing thermal from non-thermal contributions to plasmonic hydrodefluorination. Nat Catal 5, 247–250 (2022). https://doi.org/10.1038/s41929-022-00768-5

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