Fenton-Inactive Cd Enables Highly Selective O(2)-Derived Domino Reaction

芬顿惰性镉可实现高选择性的O₂衍生多米诺反应

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Abstract

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 d(10)s(2) 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 Cd(0) to Cd(δ+), facilitating electron localization and implementing a different electrocatalytic preference compared to conventional d(10)-electron configurations. The resulting Cd(B) catalyst demonstrates high selectivity (>90% on average) in the O(2)-to-H(2)O(2) conversion, negligible activity loss over 100 h, and a superior H(2)O(2) production rate (15.5 mol∙g(cat) (-1) h(-1) at -100 mA). More unexpectedly, the in situ generated H(2)O(2) exhibits a unique advantage over commercial products, selectively oxidizing cinnamaldehyde to benzaldehyde by modulating the practical current.

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