Raman microscope equipped with a laser excitation of 532 nm and 1800
l/mm grading and coupled with a 50× objective lens (Leica). In
situ Raman study was done with 785 nm laser, 1200 l/mm grading, 50×
objective lens (Leica) in 0.1 M high-purity semiconductor-grade KOH
in homemade electrochemical cell. Au substrate was polished and roughened
following the previously reported protocol69 (link) and the sample ink solution was dropcasted on to it. The sample
ink solution consisted of 4.8 mg of catalyst, 1 mL of water: isopropanol
(3:1) mixture, and 50 uL of nafion. Pt wire and RHE were used as the
counter and reference electrodes, respectively. Argon saturated electrolyte
was used, and the flux was controlled using a peristaltic pump with
a flow rate of 1–8 mL/min in order to remove the bubble formation.
Before applying bias, the sample was immersed in electrolyte for 30
min to check the solvation effect. In situ Raman spectra were then
collected with fixed potential in the chronoamperometric (CA) mode
from 1.0 to 1.5 V vs RHE.