Photon illumination of metal nanoparticle catalysts can promote catalytic reaction rates and selectivity through charge transfer to adsorbates. Based on temperature programmed desorption measurements we observe that illumination of small catalytic metal nanoparticles by relatively low flux visible photons (&lt; 1 W/cm<sup>2</sup>) can influence the binding energy adsorbed species by up to 50 kJ/mol. We also observe that the impact of light is wavelength dependent and chemically specific, influencing some elementary step energetics more than others. This suggests that light can be used to in-situ control the binding energy of adsorbates on metal catalysts. Here we will discuss the use of pulsed light with programmable durations to promote catalytic chemistry by more than what can be achieved through static illumination. Our results suggest that using light pulses to dynamically control the binding energy of adsorbates on catalytic surfaces may enable higher activity or selectivity than is possible with static illumination or dictated by linear free energy scaling relations.

Pulsed visible photon illumination for promoting and controlling catalytic chemistry on metal nanoparticles

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ACS Fall 2022

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