Study on Development of Hydrogen Peroxide Generation Reactor with Pin-to-Water Atmospheric Discharges

We present an experimentally validated, engineering-oriented framework for the design and operation of pin-to-water (PTW) atmospheric discharges to produce hydrogen peroxide (H₂O₂) on demand. Motivated by industrial needs for safe, point-of-use oxidant supply, we combine time-resolved diagnostics (FTIR, OES), liquid-phase analysis (ion chromatography, pH, conductivity), and coupled plasma-chemistry/fluid simulations to link plasma state to aqueous H₂O₂ yield. Under the tested conditions (14.3 kHz, 0.2 kW; electrode to quartz wall distance 12–14 mm; coolant setpoints 0–40 °C), H₂O₂ concentration follows a reproducible non-monotonic trajectory: rapid accumulation during the early treatment (typical peak at ~15–25 min), followed by decline with continued operation. The decline coincides with a robust vibrational-temperature (T_vib) threshold near ~4900 K measured from N₂ emission, and with concurrent NO_X accumulation and bulk acidification. Global chemistry modeling and Fluent flow fields reproduce the observed trend and show that both vibrational excitation (kinetics) and convective transport (mass/heat transfer) determine the productive time window. Based on these results, we formulate practical design rules—electrode gap (power density), discharge current control, thermal/flow management, water quality, and OES-based T_vib monitoring with an automated stop rule—that maximize H₂O₂ yield while avoiding NO_X-dominated suppression. The study provides a clear path for transforming mechanistic plasma insights into deployable, industrial H₂O₂ generator designs.