Catalytic Oxidation Mechanisms Using Gold Nanoparticles

Gold nanoparticles have emerged as highly active catalysts for oxidation reactions under mild conditions, challenging the long-held view that gold is inert. Their activity is governed by the interplay of particle size, shape and the nature of the supporting oxide, which together define the availability of active oxygen species, the pathways for oxygen activation and the stability of reaction intermediates. Mechanistic assessments have revealed that both Langmuir–Hinshelwood and Mars–van Krevelen routes can operate, depending on the support and the presence of promoters such as water. Metal–support interactions modulate the electronic structure of the gold clusters, while defects and oxygen vacancies on reducible oxides facilitate oxygen dissociation and replenishment. Under reaction conditions, morphological adjustments of the nanoparticles at the metal–oxide interface create dynamic ensembles of perimeter sites that govern CO oxidation, selective oxidation of organic substrates and the in situ generation of reactive oxygen species. The global significance of this field extends to environmental catalysis for pollutant abatement, selective oxidation in fine chemical production and the development of cleaner energy systems.

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Catalytic Oxidation Mechanisms Using Gold Nanoparticles publication trend

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Technical terms

Mars–van Krevelen mechanism: A pathway in which lattice oxygen from the support oxidises the substrate, creating an oxygen vacancy that is subsequently refilled by molecular O₂.

Langmuir–Hinshelwood mechanism: A surface reaction mechanism in which both reactants adsorb on the catalyst surface and react to form products before desorption.

Metal–support interaction: Electronic and structural effects at the interface between metal nanoparticles and oxide supports that influence catalytic activity and stability.

Operando spectroscopy: In situ analytical techniques performed under working reaction conditions to monitor catalyst structure and chemistry in real time.

Oxygen vacancy: A defect site in an oxide lattice lacking an oxygen atom, often serving as a reactive centre for oxygen activation and substrate adsorption.

References

1. A Water-Promoted Mars−van Krevelen Reaction Dominates Low-Temperature CO Oxidation over Au-Fe2O3 but Not over Au-TiO2. ACS Catalysis (2024).
2. CO oxidation over supported gold nanoparticles as revealed by operando grazing incidence X-ray scattering analysis. Faraday Discussions (2018).
3. CO Oxidation Catalyzed by Au Dispersed on SBA-15 Modified with TiO2 Films Grown via Atomic Layer Deposition (ALD). Catalysts (2023).