Iron oxychloride(FeOCl)is a unique layered material with tunable electronic properties.The conventional synthetic route of chemical vapor transition involves a thermodynamics-driven gas-solid interfacial reaction whic...Iron oxychloride(FeOCl)is a unique layered material with tunable electronic properties.The conventional synthetic route of chemical vapor transition involves a thermodynamics-driven gas-solid interfacial reaction which often generates macroscopic crystals with stable facets.In this study,through analyzing the effects of the synthetic parameters on the FeOCl synthesis,we discovered the dominant contribution of theα-Fe_(2)O_(3)precursors on the chemical property of the FeOCl product,and subsequently developed a highly-controllable synthetic route of tailoring the FeOCl structures into small sizes and exposed high-energy facets via a facile and scalable mechanical-chemical approach.The synthesized products could be systematically tuned by the ball-milling conditions of theα-Fe_(2)O_(3)precursors.With increased milling time,the FeOCl crystallites demonstrated reduced sizes and more exposed(110)facets.Intriguingly,these smallsized FeOCl catalysts exhibited much faster Fenton-like kinetics than the pristine macroscopic FeOCl materials.Specifically,FeOCl catalysts with a 12-hour milling time showed nearly 39 times higher efficiency toward phenol degradation than the pristine FeOCl.The structure-reactivity relationship was further elucidated using the combinatory analysis via density functional theory calculation,electron paramagnetic resonance and radical quenching probe experiments.This work provides a rationale for tailoring the surface structures of FeOCl crystallites for potential applications in environmental catalysis.展开更多
基金This work was partially supported by the National Key Projects for Fundamental Research and Development of China(Grant No.2019YFC1906700)the National Natural Science Foundation for Outstanding Young Scholars(Grant No.22222602)the National Natural Science Foundation of China(Grant No.21876049).
文摘Iron oxychloride(FeOCl)is a unique layered material with tunable electronic properties.The conventional synthetic route of chemical vapor transition involves a thermodynamics-driven gas-solid interfacial reaction which often generates macroscopic crystals with stable facets.In this study,through analyzing the effects of the synthetic parameters on the FeOCl synthesis,we discovered the dominant contribution of theα-Fe_(2)O_(3)precursors on the chemical property of the FeOCl product,and subsequently developed a highly-controllable synthetic route of tailoring the FeOCl structures into small sizes and exposed high-energy facets via a facile and scalable mechanical-chemical approach.The synthesized products could be systematically tuned by the ball-milling conditions of theα-Fe_(2)O_(3)precursors.With increased milling time,the FeOCl crystallites demonstrated reduced sizes and more exposed(110)facets.Intriguingly,these smallsized FeOCl catalysts exhibited much faster Fenton-like kinetics than the pristine macroscopic FeOCl materials.Specifically,FeOCl catalysts with a 12-hour milling time showed nearly 39 times higher efficiency toward phenol degradation than the pristine FeOCl.The structure-reactivity relationship was further elucidated using the combinatory analysis via density functional theory calculation,electron paramagnetic resonance and radical quenching probe experiments.This work provides a rationale for tailoring the surface structures of FeOCl crystallites for potential applications in environmental catalysis.
