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Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

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Distinct Kinetic Signatures of Photodesorption from Metal Nanoparticles.

Arik Beck^1,2, Michael J Gordon¹, Phillip Christopher¹

¹Department of Chemical Engineering, University of California─Santa Barbara, Santa Barbara, California 93106, United States.

Journal of the American Chemical Society

|February 12, 2026

Summary

Visible light influences catalytic reactions on metal nanoparticles. This study shows photons drive CO desorption independently of thermal energy, establishing a new kinetic framework for photocatalysis and catalyst design.

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Published on: February 11, 2016

Area of Science:

Heterogeneous catalysis
Surface science
Photochemistry

Background:

Photon fluxes impact metal nanoparticle catalysis rates and selectivity.
Existing models use empirical photon-dependent kinetic parameters, hindering mechanistic understanding.
This approach conflicts with fundamental photochemistry principles from surface science.

Purpose of the Study:

To investigate the influence of visible photon flux on CO adsorption-desorption on Pt/Al2O3 catalysts.
To develop a mechanistic kinetic model for photon-driven desorption.
To reconcile surface science observations with applied catalysis.

Main Methods:

Utilized 440 nm photon flux and in situ IR spectroscopy to measure CO* coverages on Pt/Al2O3.
Studied reactions under isothermal and isobaric conditions across a temperature range (473-573 K).
Developed and validated a kinetic model incorporating independent thermal and photon-induced desorption pathways.

Main Results:

Steady-state CO* coverage decreased with increasing photon flux, indicating photon-driven desorption.
Photon flux effects on CO* coverage were largely temperature-independent.
A kinetic model accurately described CO* coverages, revealing distinct parameters for photon-driven desorption from different Pt sites.

Conclusions:

Photon fluxes can drive catalytic reactions out of thermal equilibrium.
Established a general kinetic framework for photon-driven processes on metals.
Provides design principles for catalysts, reactions, and photon fluxes to optimize photocatalysis.