Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-inv...Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.展开更多
基金supported by the National Natural Science Foundation of China (NSFC,Nos.12474274,92161101)the Innovation Project of Jinan Science and Technology Bureau(No.2021GXRC032)the Natural Science Foundation of Shandong Province (No.ZR2024MA091)。
文摘Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.
