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.

由局部表面等离子体激元共振的衰减产生的热载流子（电子和空穴）在金属纳米颗粒的催化反应中起主要作用。通过获得对-氨基硫酚的表面增强拉曼散射（SERS）光谱，该对氨基苯酚是热电子还原对硝基硫酚的产物，对于银，金和铜的纳米颗粒，这里显示出不同的催化活性。作为主要发现，发现包括卤化物和非卤化物的一系列不同的配体在所有三种金属的纳米粒子的还原反应中增强了产物的形成。与具有和不具有配体的金属的标准电极电势进行比较，以及在不同电极电势下获得的SERS数据表明，较高的催化活性与较高的费米能级有关，从而提高了热载流子产生的效率。由于增强的电子收集，这种配体增强的热电子还原的概念提供了一种使光化学能转换效率更高的方法。