Title: Functionalization of zeolite-encapsulated Cu₅ clusters as visible-light photoactive subnanomaterials

Authors: Katarzyna M. Krupka, Lenard L. Carroll and María Pilar de Lara-Castells

DOI: https://doi.org/10.1039/D4RA08633C

Date: 22/01/2025

Working Group: WG1, WG3

Grant Period: 2

Grant Period Goal (number): GAPG-3, GAPG-5

Covered deliverables from the MoU (number): 1,3

Countries involved: Spain, Poland

Number of female/young/ITC coauthors: 3/2/1

Abstract: The unique structural properties of zeolites make them ideal environments for encapsulating subnanometric metal clusters on their microporous channels and cavities, showing an enhanced catalytic performance. As a first step towards the functionalization of these clusters as photocatalysts as well, this work addresses the optical properties of zeolite-encapsulated Cu₅–TiO₂ nanoparticles as well as their application in the photo-induced activation of CO₂ by sunlight. Model density functional theory (DFT) calculations indicate the stability of the Cu₅ cluster adsorbed on the TiO₂ nanoparticles filling the pores of a model zeolite structure. Second, it is shown that while TiO₂ nanoparticles absorb in the UV, the photo-absorption spectrum of the Cu₅–TiO₂ nanoparticle composite is peaked at the visible region, where the sun has its maximum energy input, also allowing for the photo-induced activation of CO₂ adsorbed onto the Cu₅ cluster.