Precursor-driven structural tailoring of iron oxychloride for enhanced heterogeneous Fenton activity

doi:10.1007/s11705-023-2330-z

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (10) : 1533-1543 https://doi.org/10.1007/s11705-023-2330-z

RESEARCH ARTICLE

Precursor-driven structural tailoring of iron oxychloride for enhanced heterogeneous Fenton activity

Shengshuo Xu¹, Zhenying Lu¹, Jinling Wang^1,², Guangtuan Huang¹, Hualin Wang^1,², Xuejing Yang^1,²(

)

¹. National Engineering Laboratory for Industrial Wastewater Treatment, East China University of Science and Technology, Shanghai 200237, China
². State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

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Abstract

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 the α-Fe₂O₃ 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 the α-Fe₂O₃ precursors. With increased milling time, the FeOCl crystallites demonstrated reduced sizes and more exposed (110) facets. Intriguingly, these small-sized 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.

Keywords FeOCl mechanical activation heterogeneous Fenton reaction ball milling

Corresponding Author(s): Xuejing Yang

Just Accepted Date: 26 May 2023 Online First Date: 31 July 2023 Issue Date: 07 October 2023

Cite this article:

Shengshuo Xu,Zhenying Lu,Jinling Wang, et al. Precursor-driven structural tailoring of iron oxychloride for enhanced heterogeneous Fenton activity[J]. Front. Chem. Sci. Eng., 2023, 17(10): 1533-1543.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2330-z
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I10/1533

Fig.1 The particle size information and morphology structure of different α-Fe₂O₃. (a) Characterization of α-Fe₂O₃ particle size at a different grinding time; (b) XRD pattern of α-Fe₂O₃ with different grinding times and Williamson–Hall curve of α-Fe₂O₃ at different milling times (β_f represents the integral breadths; d is the interplanar spacing); (c) the FTIR shift of Fe–O vibration with different milling time; (d) the path diagram of the structural evolution of α-Fe₂O₃ particles by ball-milling, showing structural disordering with increasing defects and lattice strains; (e) gaseous form of ferric chloride dimer and the attachment of gaseous ferric chloride onto the surface of hematite to form FeOCl monomers.

Fig.2 Structure and morphology of FeOCl. Schematic diagram of the exposed crystal surface, morphology, configuration, selected area electron diffraction and the TEM image of (a) FeOCl-P and (b) FeOCl-12 h.

Fig.3 (a) Activity of different FeOCl for degradation of phenol and the number of pollutants degraded per unit specific surface area (q/S_BET); (b) EPR signals obtained in water (pH = 4) containing 180 mmol·L^–1 DMPO + 500 mg·L^–1 FeOCl + 30 mmol·L^–1 H₂O₂; (c) degradation experiment of pCBA as a hydroxyl radical probe; (d) effects of radical scavengers on phenol degradation and the stoichiometric efficiency of H₂O₂ as a function of reaction time over different FeOCl (Reaction conditions: phenol concentration of 50 mg·L^?1; catalyst dosage of 500 mg·L^?1; pCBA concentration of 0.06 mmol·L^–1; H₂O₂ amount of 30 mmol·L^–1; pH = 4.0 (4 mmol·L^–1 HAc-NaAc); 25 °C).

Fig.4 The calculation model of H₂O₂ adsorbed on different crystalline facets of FeOCl: (a) (010), (b) (101) and (c) (110) facet; (d) comparison of adsorption energy and bond length changes after H₂O₂ adsorption over FeOCl in different H₂O₂ steric hindrance.

Fig.5 Proposed mechanism for the pollutants oxidative catalyzed by FeOCl-12 h.

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