Identifying signatures of thermal and non-thermal reaction pathways in plasmon induced H2 + D2 exchange reaction

04 January 2022, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


In this work we demonstrate a strategy for identifying experimental signatures of thermal and non-thermal effects in plasmon mediated heterogeneous catalytic chemistry, a topic widely debated and discussed in the literature. Our method is based on monitoring the progress of plasmon-induced (or thermally-driven) reaction, carried out in a closed system, all the way to equilibrium. Initial part of evolution of the reaction provides information about kinetics, whereas at later times the equilibrium concentrations provide information about effective temperature at the reaction sites. Combining these two pieces of information we estimate the activation energies. Using this strategy on H 2 (g) + D 2 (g) <-->2 HD(g) isotope exchange reaction, catalyzed by Au nanoparticles under thermally-driven and light-induced conditions, we estimate the activation energies to be 0.75 ± 0.02 eV and 0.21 ± 0.02 eV, respectively. These vastly different activation energies observed are interpreted as a signature of different reaction pathways followed by the system under thermally-driven and light-induced conditions.


heterogeneous catalysis
hot carrier

Supplementary materials

Identifying signatures of thermal and non-thermal reaction pathways in plasmon induced H 2 + D 2 exchange reaction – Supporting Information
SI-1: Diffused reflectance spectrum of Au nanoparticles supported on silica SI-2: Estimating temperatures from equilibrium constant measurements SI-3: Background HD contribution to the reaction SI-4: Estimating gas dependent sensitivity factors for our detection setup SI-5: Second order kinetics model used for fitting


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