Visualization and Quantification of Electrochemical H₂ Bubble Nucleation at Pt, Au, and MoS₂ Substrates

Electrolytic gas evolution is a significant phenomenon in many electrochemical technologies from water splitting, chloralkali process to fuel cells. Although it is known that gas evolution may substantially affect the ohmic resistance and mass transfer, studies focusing on the electrochemistry of individual bubbles are critical but also challenging. Here, we report an approach using scanning electrochemical cell microscopy (SECCM) with a single channel pipet to quantitatively study individual gas bubble nucleation on different electrode substrates, including conventional polycrystalline Pt and Au films, as well as the most interesting two-dimensional semiconductor MoS₂. Due to the confinement effect of the pipet, well-defined peak-shaped voltammetric features associated with single bubble nucleation and growth are consistently observed. From stochastic bubble nucleation measurement and finite element simulation, the surface H₂ concentration corresponding to bubble nucleation is estimated to be ∼218, 137, and 157 mM, with critical nuclei contact angles of ∼156°, ∼161°, and ∼160° at polycrystalline Pt, Au, and MoS₂ substrates, respectively. We further demonstrated the surface faceting at polycrystalline Pt is not specifically correlated with the bubble nucleation behavior.