Enhancing the performance of hydrogen peroxide electrosynthesis via anode-cathode coupling and pulsed electrolysis

Abstract

Enhancing the electrosynthesis of hydrogen peroxide (H₂O₂) (the two-electron oxygen reduction and 2e⁻ORR) is critical for decentralized and on-site H₂O₂ production. However, the high aeration energy consumption and serious side reactions in the 2e⁻ORR system have decreased its 2e⁻ORR performance, hindering its further application. Herein, we greatly reduced the aeration energy consumption using anode-produced O₂ for the cathode 2e⁻ORR (anode-cathode coupling) and further decreased the hydrogen evolution reaction (HER) and H₂O₂ electroreduction by applying pulses. A flow-through reactor with narrow electrode gaps efficiently improves the utilization of anode-produced O₂. It increased the effluent H₂O₂ concentration by 101.22% compared to non-coupled systems. In addition, pulsed electrolysis increased the effluent H₂O₂ concentration and current efficiency by 3.41 and 11.38 times, respectively. During the power-off period, the electrochemical reaction paused, whereas the O₂ and H₂O₂ diffusion continued under the concentration gradient. These processes relieve the O₂ shortage at the cathodes to decrease the HER and alleviate H₂O₂ accumulation at the cathodes, thus reducing its decomposition. Our results provide an easy and efficient way to improve H₂O₂ electrosynthesis performance.

Graphical abstract

Keywords

In situ hydrogen peroxide production / Anodic oxygen utilization / Pulsed electrolysis / Interfacial engineering / Mass transfer

Highlight

	● Anodic O2 is used for cathode 2e−ORR in anode-cathode coupling.
	● Flow-through reactor with narrow electrode gaps boosts O2 utilization.
	● Pulsed electrolysis decreases HER and H2O2 electroreduction.
	● In Operando visualization shows how pulses reduce concentration polarization.

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