In situ surface-enhanced Raman scattering shows ligand-enhanced hot electron harvesting on silver, gold, and copper nanoparticles

• Published in: Journal of catalysis Vol. 383; pp. 153 - 159
• Main Authors: Zhang, Zhiyang, Li, Yawei, Frisch, Johannes, Bär, Marcus, Rappich, Jörg, Kneipp, Janina
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.03.2020
• Subjects: Hot electrons; Ligands; p-Aminothiophenol; p-Nitrothiophenol; SERS; p-Aminothiophenol; Ligands; Hot electrons; SERS; p-Nitrothiophenol
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2020.01.006

[Display omitted] •The six-electron reduction of PATP to PNTP by hot electrons occurs on Au, Ag and Cu nanoparticles.•The reactions are enhanced by ligands due to an increase of the metal nanoparticles’ Fermi level.•Ligand-enhanced hot electron reduction provides a way to improved light-to-chemical energy conversion. Hot carriers (electrons and holes) generated from the decay of localized surface plasmon resonances can take a major role in catalytic reactions on metal nanoparticles. By obtaining surface enhanced Raman scattering (SERS) spectra of p-aminothiophenol as product of the reduction of p-nitrothiophenol by hot electrons, different catalytic activity is revealed here for nanoparticles of silver, gold, and copper. As a main finding, a series of different ligands, comprising halide and non-halide species, are found to enhance product formation in the reduction reaction on nanoparticles of all three metals. A comparison with the standard electrode potentials of the metals with and without the ligands and SERS data obtained at different electrode potential indicate that the higher catalytic activity can be associated with a higher Fermi level, thereby resulting in an improved efficiency of hot carrier generation. The concept of such a ligand-enhanced hot electron reduction provides a way to make light-to-chemical energy conversion more efficient due to improved electron harvesting.