Harvesting the challenges of plasmon-enhanced electrochemistry: Perspectives on an intricated research field

Plasmon-enhanced electrochemistry merges light-matter interactions with interfacial charge transfer. This simple definition can obscure the field’s complexity: electrochemistry already deals with a dynamic, often poorly understood electrode-electrolyte interface, and adding light introduces a whole new layer of complexity. The appeal of coupling plasmonics with electrochemistry relies on the fact that optical-electrical co-design can modulate rates, selectivity, and detection limits. In this Perspective, we briefly outline the mechanisms by which light can modify an electrochemical output (near-field enhancement, hot carrier generation, and thermalization) and recast the often-dismissed photothermal channel as a controllable knob to boost activity and even steer selectivity. We note that the field has ample proof-of-principle, but advancing it now demands proof-of-mechanism, enabling rational control of wavelength, nanoparticle geometry, interfacial energetics, and photothermal inputs to predictably modulate rates and selectivity