Amino-induced cleavage of the electron-communicating S-bridge to unlock mixed-valence copper for potent oxidase-like catalysis and selective sensing.

ABSTRACT: Transition-metal sites with mixed valence often coexist in diverse catalysts, yet their precise roles remain elusive. Taking a thiadiazole-coordinated Cu nanozyme system as an example, we developed ligand side-group engineering to modulate adjacent dicopper sites with different mixed Cu¹⁺/Cu²⁺ states. Amino functionalization of the ligand induced the cleavage of the electron-communicating S-bridge connecting adjacent copper centers, allowing precise manipulation of the ratio of mixed Cu¹⁺/Cu²⁺ sites. Such a tailored mixed-valence composition accelerated the preferential and selective activation of O₂ to O₂˙^- through the synergistical mechanism of Cu²⁺-dominated adsorption of O₂ and Cu^1+<

SUBMITTER: Li B 

PROVIDER: S-EPMC12272721 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature