Carbon-Caged-Yttria Catalysts for Stable Electrosynthesis of H2O2 in Concentrated Acid

The electrosynthesis of hydrogen peroxide (H2O2), with renewable electricity, air, and water as inputs, offers a sustainable alternative to the conventional anthraquinone process. Performing H2O2 electrosynthesis in concentrated acid offers advantages in functionality and energy efficiency over alkaline media yet is currently limited by short longevity. Here, we first investigate the origins of performance loss of oxidized carbon, a proven catalyst for H2O2 electrosynthesis, and observe its gradual reduction to pristine carbon during acidic electrolysis. This inspires us to design a catalyst that can stabilize the oxidized carbon sites via strong Y–O–C coordination─a strategy we instantiate via carbon-caged-yttria (C@Y2Ox) catalysts. In acids, the C@Y2Ox catalyst sustains a H2O2 selectivity of 97% after 10,000 cycles. Integrated into a gas diffusion electrode and operated in concentrated acids of pH < 0, the C@Y2Ox catalyst delivers a partial current density of ∼100 mA cm–2 at −0.4 V versus RHE over 100 h in a flow cell. Using quasi in situ NAP-XPS, operando FT-IR, and theoretical calculations, we elucidate that coordination with yttrium energetically suppresses the breakage of the O–C bond and accordingly preserves the oxidized carbon sites for selective and long-term electrosynthesis of H2O2.