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Samantha Stobbe, Ravi Teja A. Tirumala, Sundaram Bhardwaj Ramakrishnan, Marimuthu Andiappan*,

School of Chemical Engineering, Oklahoma State University, Stillwater, OK, USA

The field of nanocatalysis has been attracted in recent years by plasmonic metal nanostructures (PMNs). These metals exhibit plasmonic Mie resonance driven by localized surface plasmonic resonance (LSPR). The materials that largely fall into this category are Au, Ag, Cu, and Al. While significant progress has been made in these materials for a wide range of applications such as photovoltaics, photocatalysis, etc. due to their strong enteric-field enhancement with light interaction. However, PMNs suffer from heat losses, a low lifetime of charge carriers, and scalability issues for high-volume manufacturing. Here, we present an alternative to PMNs with dielectric Mie resonators nanoparticles (MRNPs), which are medium-to-high refractive indexed metal-oxide nanostructures such as Cu₂O, CuO, α-Fe₂O₃, CeO₂ TiO₂, etc. All these materials exhibit dielectric Mie resonance resulting in both electric and magnetic field enhancements almost of equal magnitude. In this work, we chose Copper (Cu)-based MRNPs namely Cu2O for pharmaceutically relevant coupling reactions. The choice of Cu₂O is due to previous work done by Andiappan and coworkers on the same.¹ In this work, we hybridize MRNPs (HMRNPs) with catalytically active materials such as palladium (Pd) to form Cu₂O-Pd. To test the efficacy of these HMRNPs we used an oxidative homocoupling of phenylacetylene (PA) as the probe reaction. We see around a 50% higher rate of enhancement under light compared to dark conditions.² This idea can be extended to a wide range of industrially important reactions such as CO₂ reduction, ammonia synthesis, chemicals, and fuels.

References

(1) Addanki Tirumala, R. T.; P. Dadgar, A.; Mohammadparast, F.; Ramakrishnan, S. B.; Mou, T.; Wang, B.; Andiappan, M. Homogeneous versus Heterogeneous Catalysis in Cu₂O-Nanoparticle-Catalyzed C–C Coupling Reactions. Green Chem. 2019, 21 (19), 5284–5290. https://doi.org/10.1039/C9GC01930H.

(2) Stobbe, S.; Tirumala, R. T. A.; Ramakrishnan, S. B.; Andiappan, M. Visible Light-Driven C-C Coupling Reaction of Terminal Alkynes at Atmospheric Temperature and Pressure Reaction Conditions Using Hybrid Cu₂O-Pd Nanostructures. arXiv September 9, 2022. https://doi.org/10.48550/arXiv.2209.04568.