Understanding the role of transition metal single-atom electronic structure in oxysulfur radical-mediated oxidative degradation  

作　　者：Guanshu Zhao Jing Ding Jiayi Ren Qingliang Zhao Chengliang Mao Kun Wang Jessica Ye Xueqi Chen Xianjie Wang Mingce Long 

机构地区：[1]State Key Laboratory of Urban Water Resources and Environment,School of Environment,Harbin Institute of Technology,Harbin,150090,China [2]Solar Fuels Group,Department of Chemistry,University of Toronto,80 St.George Street,Toronto,Ontario,M5S 3H6,Canada [3]School of Physics,Harbin Institute of Technology,Harbin,150001,China [4]School of Environmental Science and Engineering,Key Laboratory of Thin Film and Microfabrication Technology(Ministry of Education),Shanghai Jiao Tong University,800 Dongchuan Road,Shanghai,200240,China

出　　处：《Environmental Science and Ecotechnology》2024年第4期247-258,共12页环境科学与生态技术（英文）

基　　金：Financial support from the National Natural Science Foundation of China(52270068);the open Project of the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(QG202225);the Heilongjiang Touyan Innovation Team Program was highly appreciated;We would also like to thank Dr.Shibo Xi of Singapore Synchrotron Light Source for his help in catalyst characterization.

摘　　要：The ubiquity of refractory organic matter in aquatic environments necessitates innovative removal strategies.Sulfate radical-based advanced oxidation has emerged as an attractive solution,offering high selectivity,enduring efficacy,and anti-interference ability.Among many technologies,sulfite activation,leveraging its cost-effectiveness and lower toxicity compared to conventional persulfates,stands out.Yet,the activation process often relies on transition metals,suffering from low atom utilization.Here we introduce a series of single-atom catalysts(SACs)employing transition metals on g-C_(3)N_(4)substrates,effectively activating sulfite for acetaminophen degradation.We highlight the superior performance of Fe/CN,which demonstrates a degradation rate constant significantly surpassing those of Ni/CN and Cu/CN.Our investigation into the electronic and spin polarization characteristics of these catalysts reveals their critical role in catalytic efficiency,with oxysulfur radical-mediated reactions predominating.Notably,under visible light,the catalytic activity is enhanced,attributed to an increased generation of oxysulfur radicals and a strengthened electron donation-back donation dynamic.The proximity of Fe/CN's d-band center to the Fermi level,alongside its high spin polarization,is shown to improve sulfite adsorption and reduce the HOMO-LUMO gap,thereby accelerating photo-assisted sulfite activation.This work advances the understanding of SACs in environmental applications and lays the groundwork for future water treatment technologies.

关 键 词：Single-atom catalysts(SACs) Oxysulfur radical Sulfite activation Spin polarization Electronic structure 

分 类 号：X703[环境科学与工程—环境工程]