Amino‐Induced Modulation of Electronic State and Neighboring Site Distance through Second Shell Boosted Catecholase‐Mimicking Activity of Electron‐Rich Cu Center

Boosting the biomimetic catalytic activity of nanozyme is important for its potential application. One common strategy to achieve this goal mainly focused on manipulating the electronic state of metal site through the first coordination shell to modulate the adsorption/desorption strength of related reactant, intermediate and/or product, but remained challenging. Taking Cu‐based catecholase‐mimicking nanozyme for example, this work herein reports a different strategy involving amino‐induced modulation of electronic state through the second shell to raise the electron density of Cu site, which further triggers the repulsion effect between neighboring geminal Cu centers to increase the Cu─Cu distance. The resulting nanozyme with electron‐rich Cu site (DT‐Cu) presents a lower work function and an upshifted d‐band center in comparison with its counterpart (i.e., relatively electron‐deficient TA‐Cu), which promotes the electron transfer and enhances the adsorption strengths of Cu site for O2, catechol and H2O2 intermediate. The longer Cu─Cu distance of DT‐Cu accelerated the O─O bond dissociation of H2O2 intermediate. This expedites the oxygen reduction process during catecholase‐like catalysis, which together with the enhanced O2/H2O2/catechol adsorption corporately boosts the catecholase‐like activity of DT‐Cu. Amino group remotely induces the reconstruction of electronic state and neighboring site distance through second shell to boost catecholase‐mimicking activity of electron‐rich Cu‐based nanozyme.