A Bubble-STORM Approach for Super-Resolved Imaging of Nucleation Sites in Hydrogen Evolution Reactions

Stochastic optical reconstruction microscopy (STORM) is a powerful strategy to achieve super-resolved imaging of biological structures by virtue of the stochastic photoactivation of fluorophores and superlocalization algorithm. Herein, we report a fluorophore-free bubble-STORM approach for super-resolved imaging of nucleation sites in hydrogen evolution reactions (HER). When applying an appropriate pulse potential to the electrode, rapid electro-reduction of protons created a local oversaturation of hydrogen molecules and thus the nucleation of sparsely distributed hydrogen nanobubbles. A surface plasmon resonance microscopy was employed to monitor the process and report the localization of each nanobubble via superlocalization fitting. The withdrawal of electrode potential, or the microconvection, led to the immediate disappearance of nanobubbles and recovered the electrode surface before the next pulse. By repeating the procedures for thousands of cycles, one was able to reconstruct a map of nucleation sites with a spatial resolution beyond the optical diffraction limit. This approach does not require a model fluorogenic reaction or fluorescent labeling to the nanobubbles, thus revealing the intrinsic nucleation sites in the natural states. Our results further indicated the fast growth, coalescence, and detachment behaviors of nanobubbles on a time scale of sub-milliseconds, underscoring the significance of high temporal resolution for studying nanobubble nucleation.