D-band center coordination modulated enzyme-like activity in Fe-Cu dual-metal single-atom nanozymes  

作　　者：Ling Liu Shaofang Zhang Guo Li Yadong Zhe Jiamin Liu Xinxu Zhang Jiahao Wei Xin Sun Yonghui Li Xiao-Dong Zhang 

机构地区：[1]Tianjin Key Laboratory of Brain Science and Neural Engineering,Academy of Medical Engineering and Translational Medicine,Tianjin University,Tianjin 300072,China [2]Department of Physics and Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparing Technology,School of Sciences,Tianjin University,Tianjin 300350,China

出　　处：《Nano Research》2024年第7期5872-5883,共12页纳米研究（英文版）

基　　金：supported by the National Key Research and Development Program of China(Nos.2021YFF1200700 and 2021YFF1200701);the National Natural Science Foundation of China(Nos.91859101,81971744,U1932107,82001952,11804248,82302361,and 82302381);Outstanding Youth Funds of Tianjin(No.2021FJ-0009);STI 2030-Major Projects(No.2022ZD0210200);National Natural Science Foundation of Tianjin(Nos.19JCZDJC34000,20JCYBJC00940,21JCYBJC00550,21JCZDJC00620,and 21JCYBJC00490);the Key Projects of Tianjin Natural Fund(No.21JCZDJC00490);the Innovation Foundation of Tianjin University,China Postdoctoral Science Foundation(No.2023M732601);CAS Interdisciplinary Innovation Team(No.JCTD-2020-08).

摘　　要：After explorations in a diversity of single-atom nanozymes(SAzymes),developing dual-centered SAzymes becomes a promising approach for superior catalytic performance.But confusing mechanisms including atomic coordination,spatial configuration,and metal–metal atom interaction hinder the development and design of SAzymes.Herein,a dual-centered Fe-Cu-N_(x)SAzyme exhibits excellent peroxidase(POD)-and catalase(CAT)-like activities with d-band center(ε_(d))coordination of Fe and Cu in multiple reaction stages,which plays a critical role in the adsorption of H_(2)O_(2)molecule and H_(2)O and O_(2)release.Therefore,the dband center coordination,which can be represented byε_(d)(Fe)–ε_(d)(Cu)shifts,leads to the competition between one-side and bilateral adsorption,which determines the favorable reaction path with lower energy barriers.Based on experimental statistics,simulated formation energies,and reaction barriers,3 configurations,Fe-Cu-N6-I,Fe-Cu-N_(8)-II,and Fe-Cu-N_(8)-III,are modeled and validated.Impressively,configuration-dependent catalytic selectivity and the competition between one-side and bilateral adsorption can be unveiled by d-band center coordination paradigm analysis.Theoretical simulations suggest that the unsymmetrical charge distribution over the three Fe-Cu configurations could tune the adsorption strength compared with the counterparts FeN_(4)and CuN_(4).The present work provides a potential route for optimizing enzyme-like catalysis by designing the dual-or even triple-metal SAzymes,which demonstrates the large space to modulate the metal atomic configuration and interaction.

关 键 词：single-atom catalysis Fe-Cu dual-metal d-band center coordination enzyme mimicking competitive adsorption mechanisms 

分 类 号：O64[理学—物理化学]