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Iron 3D-Orbital Configuration Dependent Electron Transfer for Efficient Fenton-Like Catalysis
Yijie Wu1, Xin Wang2, Tiantian She1
1School of Environment, Jiangsu Engineering Lab of Water and Soil Eco-remediation, Nanjing Normal University, Nanjing, 210023, P. R. China.
Small (Weinheim an Der Bergstrasse, Germany)
|September 2, 2023
Summary
Iron catalysts with specific d-orbital configurations activate peroxymonosulfate (PMS) for water treatment. Octahedral iron sites in ZnFe2O4 show higher activity and produce nonradical reactive oxygen species (ROS) for efficient pollutant removal.
Area of Science:
- Materials Science
- Environmental Chemistry
- Catalysis
Background:
- Transition metals are key for activating peroxymonosulfate (PMS) in water treatment.
- Understanding the electronic structures that govern PMS activation mechanisms is crucial but challenging.
- Spinel ferrites offer tunable active sites for catalytic applications.
Purpose of the Study:
- To investigate the influence of d-orbital configurations on iron sites (octahedral vs. tetrahedral) in spinel ferrites for PMS activation.
- To correlate electronic structure with catalytic activity and reactive oxygen species (ROS) generation for tetracycline removal.
- To elucidate the reaction mechanism of PMS activation by different iron coordination environments.
Main Methods:
- Synthesis of spinel ferrites ZnFe2O4 and FeAl2O4 with distinct iron d-orbital configurations.
- Evaluation of catalytic activity for tetracycline removal via PMS activation.
- Magnetic spectroscopic analysis to determine charge, spin state, and orbital arrangement.
- Quenching experiments to identify predominant ROS.
- Electrochemical measurements and Density Functional Theory (DFT) calculations.
Main Results:
- ZnFe2O4 (FeOh) exhibited higher specific activity (136.58 min⁻¹ F⁻¹ cm²) than FeAl2O4 (FeTd) (97.47 min⁻¹ F⁻¹ cm²) for tetracycline degradation.
- FeOh sites in ZnFe2O4 preferentially produced singlet oxygen (¹O₂), while FeTd sites in FeAl2O4 generated superoxide radicals (O₂•⁻).
- FeOh demonstrated superior valence transformation and interfacial electron transfer capabilities compared to FeTd.
- DFT calculations confirmed that octahedral d-orbital configuration enhances Fe-O covalence for efficient electron exchange.
Conclusions:
- The d-orbital configuration of iron sites significantly impacts PMS activation pathways and efficiency.
- Octahedral Fe sites in ZnFe2O4 are more effective for PMS activation, yielding nonradical ROS and superior catalytic performance.
- This study provides a descriptor based on d-orbital configuration for designing advanced catalysts for water treatment.
Keywords:
d-orbital configurationinterface kineticsiron-based spinelmagnetic momentumperoxymonosulfateMore Related Videos
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