Competition between Hot Carriers and Surface Electrochemistry in Gold Nanorod Dissolution

Plasmonic nanostructures have the potential to revolutionize photocatalysis by harnessing hot carriers to drive novel chemical reactions. Precise control of reaction sites on nanoparticles remains crucial for advancing catalyst design. The influence of hot carriers, particularly in the interplay with surface electrochemistry, needs further exploration. Employing single-particle spectroelectrochemical methods, we identify the conditions that lead to tip-preferred versus isotropic dissolution. We investigate how the applied potential, excitation laser power density, and wavelength of illumination directly direct gold nanorod dissolution. There is a competition between hot carrier localization and electrochemistry in determining the dissolution anisotropy. We observe that higher potentials favor isotropic dissolution, whereas higher laser power densities drive tip-specific dissolution. The results provide new insights into the control of tuning the gold nanoparticle dissolution anisotropy.