Bimetallic Synergy in Oxygen Reduction: How Tailored Metal–Metal Interactions Amplify Cooperative Catalysis DOI
Qi‐Fa Chen, Yao Xiao,

Kai Hua

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Bimetallic cooperative catalysis, inspired by cytochrome c oxidase and multicopper oxidase, plays a crucial role in the development of four-electron oxygen reduction catalysts. The distance between metals is factor affecting effect, but its precise influence on bimetallic cooperativity selective catalysis still awaits an in-depth understanding. Herein, we employ series dicopper complexes with varying linkers to systematically adjust Cu···Cu for electrocatalytic reduction. Structure-activity relationship analyses reveal that catalysts shorter center exhibited significantly higher selectivity (approaching 100% BPMPDCu2 BPMANCu2) than longer (below 80% 6-HPACu2) aqueous solution (pH 7.0). Notably, catalytic activity 11 times 237 faster those 6-HPACu2 BPMANCu2, respectively, which does not correlate directly their distances. Further investigations into low-valent LCuI2 intermediates, supported DFT calculations, indicate binding process rate-determining step under conditions sensitive CuI···CuI distance. closest BPMANCuI2 characterized strong CuI-CuI interactions more distant 6-HPACuI2 separated sites both hinder effective O2 binding. In contrast, BPMPDCuI2 maintains optimal facilitates ensures robust throughout cycle. This work underscores significance metal-metal regulation cooperatively provides valuable insights rational design high-performance

Language: Английский

Bimetallic Synergy in Oxygen Reduction: How Tailored Metal–Metal Interactions Amplify Cooperative Catalysis DOI
Qi‐Fa Chen, Yao Xiao,

Kai Hua

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Bimetallic cooperative catalysis, inspired by cytochrome c oxidase and multicopper oxidase, plays a crucial role in the development of four-electron oxygen reduction catalysts. The distance between metals is factor affecting effect, but its precise influence on bimetallic cooperativity selective catalysis still awaits an in-depth understanding. Herein, we employ series dicopper complexes with varying linkers to systematically adjust Cu···Cu for electrocatalytic reduction. Structure-activity relationship analyses reveal that catalysts shorter center exhibited significantly higher selectivity (approaching 100% BPMPDCu2 BPMANCu2) than longer (below 80% 6-HPACu2) aqueous solution (pH 7.0). Notably, catalytic activity 11 times 237 faster those 6-HPACu2 BPMANCu2, respectively, which does not correlate directly their distances. Further investigations into low-valent LCuI2 intermediates, supported DFT calculations, indicate binding process rate-determining step under conditions sensitive CuI···CuI distance. closest BPMANCuI2 characterized strong CuI-CuI interactions more distant 6-HPACuI2 separated sites both hinder effective O2 binding. In contrast, BPMPDCuI2 maintains optimal facilitates ensures robust throughout cycle. This work underscores significance metal-metal regulation cooperatively provides valuable insights rational design high-performance

Language: Английский

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