High-rate electrochemical H₂O₂ production over multimetallic atom catalysts under acidic-neutral conditions

Abstract

Hydrogen peroxide (H₂O₂) production by the electrochemical 2-electron oxygen reduction reaction (2e^- ORR) is a promising alternative to the energy-intensive anthraquinone process, and single-atom electrocatalysts show the unique capability of high selectivity toward 2e^- ORR against the 4e^- one. The extremely low surface density of the single-atom sites and the inflexibility in manipulating their geometric/electronic configurations, however, compromise the H₂O₂ yield and impede further performance enhancement. Herein, we construct a family of multiatom catalysts (MACs), on which two or three single atoms are closely coordinated to form high-density active sites that are versatile in their atomic configurations for optimal adsorption of essential ^*OOH species. Among them, the Co_x-Ni MAC presents excellent electrocatalytic performance for 2e^- ORR, in terms of its exceptionally high H₂O₂ yield in acidic electrolytes (28.96 mol L^-1 g_cat.^-1 h^-1) and high selectivity under acidic to neutral conditions in a wide potential region (>80%, 0-0.7 V). Operando X-ray absorption and density functional theory analyses jointly unveil its unique trimetallic Co₂NiN₈ configuration, which efficiently induces an appropriate Ni-d orbital filling and modulates the *OOH adsorption, together boosting the electrocatalytic 2e^- ORR capability. This work thus provides a new MAC strategy for tuning the geometric/electronic structure of active sites for 2e^- ORR and other potential electrochemical processes.

Keywords

hydrogen peroxide production / multiatom catalysts / operando X-ray adsorption spectrum / reaction mechanism tendency / structure-property relation

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