Fenton‐Inactive Cd Enables Highly Selective O₂‐Derived Domino Reaction

Advancing and deploying Fenton-inactive Cd that combines excellent catalytic activity, selectivity, and stability remains a serious challenge, predominantly owing to the difficulty in regulating the intrinsic electronic states and local geometric structures of such fully occupied d¹⁰s² configuration. In this work, a combination of experiments and theoretical calculations reveals that the incorporation of boron (B) enables the tuning of the average oxidation state of Cd⁰ to Cd^δ+, facilitating electron localization and implementing a different electrocatalytic preference compared to conventional d¹⁰-electron configurations. The resulting Cd(B) catalyst demonstrates high selectivity (>90% on average) in the O₂-to-H₂O₂ conversion, negligible activity loss over 100 h, and a superior H₂O₂ production rate (15.5 mol∙g_cat ^-1 h^-1 at -100 mA). More unexpectedly, the in situ generated H₂O₂ exhibits a unique advantage over commercial products, selectively oxidizing cinnamaldehyde to benzaldehyde by modulating the practical current.