Plasmonic catalysis for controlling selectivity in the hydrogenation of cinnamaldehyde to propylbenzene under visible‐light irradiation

Frindy, Sana, Wang, Shiqi, Sullivan–Allsop, Sam, Cai, Rongsheng, Slater, Thomas J. A. ORCID: https://orcid.org/0000-0003-0372-1551, Haigh, Sarah J. and Camargo, Pedro H. C. 2025. Plasmonic catalysis for controlling selectivity in the hydrogenation of cinnamaldehyde to propylbenzene under visible‐light irradiation. Chemistry-Sustainability-Energy-Materials , 2501054. 10.1002/cssc.202501054

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Abstract

The selective hydrogenation of α,β‐unsaturated aldehydes, such as cinnamaldehyde (CAL), into value‐added aromatic hydrocarbons like propylbenzene (PPR) remains a formidable challenge due to competing C C and C O hydrogenation pathways. Here, a plasmon‐enhanced catalytic strategy employing Au@Au3Pd core–shell nanoparticles supported on silica is reported. The catalyst features a plasmonic Au core and a 1 nm Au3Pd alloyed shell (25 at% Pd), enabling light‐driven modulation of reaction selectivity. Under visible‐light irradiation, the catalyst achieves complete CAL conversion with a ≈34% yield of PPR, corresponding to a 7.7‐fold enhancement in turnover frequency relative to dark conditions. Density functional theory calculations reveal that interfacial electronic coupling between the Au core and Pd‐rich shell upshifts the Pd d‐band center and enhances charge transfer, promoting both C C and C O hydrogenation steps followed by hydrogenolysis to PPR. This study demonstrates a robust approach to overcome selectivity limitations in multifunctional molecule hydrogenation by harnessing localized surface plasmon resonance effects. The insights gained offer a foundation for the rational design of light‐responsive bimetallic catalysts for selective and sustainable transformations.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Schools > Chemistry Research Institutes & Centres > Cardiff Catalysis Institute (CCI)
Additional Information:	License information from Publisher: LICENSE 1: URL: http://creativecommons.org/licenses/by/4.0/
Publisher:	Wiley
ISSN:	1864-5631
Date of First Compliant Deposit:	19 August 2025
Last Modified:	19 Aug 2025 10:30
URI:	https://orca.cardiff.ac.uk/id/eprint/180545

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