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

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.

Graphical abstract

Keywords

FeOCl / mechanical activation / heterogeneous Fenton reaction / ball milling

References

[1] Lind M. Refinement of the crystal structure of iron oxychloride. Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry, 1970, 26(8): 1058–1062

[2] Yang X J, Xu X M, Xu J, Han Y F. Iron oxychloride (FeOCl): an efficient Fenton-like catalyst for producing hydroxyl radicals in degradation of organic contaminants. Journal of the American Chemical Society, 2013, 135(43): 16058–16061

[3] Sun M, Zucker I, Davenport D M, Zhou X C, Qu J H, Elimelech M. Reactive, self-cleaning ultrafiltration membrane functionalized with iron oxychloride nanocatalysts. Environmental Science & Technology, 2018, 52(15): 8674–8683

[4] Sun M, Chu C H, Geng F L, Lu X L, Qu J H, Crittenden J, Elimelech M, Kim J H. Reinventing Fenton chemistry: iron oxychloride nanosheet for pH-insensitive H₂O₂ activation. Environmental Science & Technology Letters, 2018, 5(3): 186–191

[5] Zhou P, Ren W, Nie G, Li X J, Duan X G, Zhang Y L, Wang S B. Fast and long-lasting iron(III) reduction by boron toward green and accelerated Fenton chemistry. Angewandte Chemie International Edition, 2020, 59(38): 16517–16526

[6] Xiong Y, Li H C, Liu C W, Zheng L R, Liu C, Wang J O, Liu S J, Han Y H, Gu L, Qian J S, Wang D. Single-atom Fe catalysts for Fenton-like reactions: roles of different N species. Advanced Materials, 2022, 34(17): 2110653

[7] Huang X P, Chen Y, Walter E, Zong M R, Wang Y, Zhang X, Qafoku O, Wang Z M, Rosso K M. Facet-specific photocatalytic degradation of organics by heterogeneous Fenton chemistry on hematite nanoparticles. Environmental Science & Technology, 2019, 53(17): 10197–10207

[8] Liu M Y, Xu Y, Zhao Y J, Wang Z, Shi D Y. Hydroxyl radical-involved cancer therapy via Fenton reactions. Frontiers of Chemical Science and Engineering, 2022, 16(3): 345–363

[9] Zhu Y P, Zhu R L, Xi Y F, Zhu J X, Zhu G Q, He H P. Strategies for enhancing the heterogeneous Fenton catalytic reactivity: a review. Applied Catalysis B: Environmental, 2019, 255: 117739

[10] Yang X F, Wang A Q, Qiao B T, Li J, Liu J Y, Zhang T. Single-atom catalysts: a new frontier in heterogeneous catalysis. Accounts of Chemical Research, 2013, 46(8): 1740–1748

[11] Pieczko M E, Breen J J. Atomic force microscopy studies of iron oxychloride. Langmuir, 1995, 11(4): 1412–1414

[12] Hwang S R, Li W H, Lee K C, Lynn J W, Wu C G. Spiral magnetic structure of Fe in van der Waals gapped FeOCl and polyaniline-intercalated FeOCl. Physical Review B: Condensed Matter, 2000, 62(21): 14157–14163

[13] Li S S, Lin Y C, Hong J H, Gao B, Lim H E, Yang X, Liu S, Tateyama Y, Tsukagoshi K, Sakuma Y, Suenaga K, Taniguchi T. Mixed-salt enhanced chemical vapor deposition of two-dimensional transition metal dichalcogenides. Chemistry of Materials, 2021, 33(18): 7301–7308

[14] Wang D W, Gilliland S E III, Yi X B, Logan K, Heitger D R, Lucas H R, Wang W N. Iron mesh-based metal organic framework filter for efficient arsenic removal. Environmental Science & Technology, 2018, 52(7): 4275–4284

[15] Pham A L T, Lee C, Doyle F M, Sedlak D L. A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values. Environmental Science & Technology, 2009, 43(23): 8930–8935

[16] Espinosa J C, Catala C, Navalon S, Ferrer B, Alvaro M, Garcia H. Iron oxide nanoparticles supported on diamond nanoparticles as efficient and stable catalyst for the visible light assisted Fenton reaction. Applied Catalysis B: Environmental, 2018, 226: 242–251

[17] Zhu Z X, Chen Y, Gu Y, Wu F, Lu W Y, Xu T F, Chen W X. Catalytic degradation of recalcitrant pollutants by Fenton-like process using polyacrylonitrile-supported iron(II) phthalocyanine nanofibers: intermediates and pathway. Water Research, 2016, 93: 296–305

[18] Zou J, Ma J, Chen L W, Li X C, Guan Y H, Xie P C, Pan C. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine. Environmental Science & Technology, 2013, 47(20): 11685–11691

[19] Yao Y J, Cai Y M, Wu G D, Wei F Y, Li X Y, Chen H, Wang S B. Sulfate radicals induced from peroxymonosulfate by cobalt manganese oxides (Co_xMn_3−xO₄) for Fenton-like reaction in water. Journal of Hazardous Materials, 2015, 296: 128–137

[20] Yuan F, Hu C, Hu X X, Wei D B, Chen Y, Qu J H. Photodegradation and toxicity changes of antibiotics in UV and UV/H₂O₂ process. Journal of Hazardous Materials, 2011, 185(2): 1256–1263

[21] Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B: Condensed Matter, 1996, 54(16): 11169–11186

[22] Perdew J P, Zunger A. Self-interaction correction to density-functional approximations for many-electron systems. Physical Review B: Condensed Matter, 1981, 23(10): 5048–5079

[23] Klimeš J, Bowler D R, Michaelides A. Chemical accuracy for the van der Waals density functional. Journal of Physics Condensed Matter, 2009, 22(2): 022201

[24] Klimeš J, Bowler D R, Michaelides A. Van der Waals density functionals applied to solids. Physical Review B: Condensed Matter and Materials Physics, 2011, 83(19): 195131

[25] Monkhorst H J, Pack J D. Special points for Brillouin-zone integrations. Physical Review B: Solid State, 1976, 13(12): 5188–5192

[26] Zhang J, Jiao X L, Xia Y G, Liu F F, Pang Y P, Zhao X F, Chen D R. Enhanced catalytic activity in liquid-exfoliated FeOCl nanosheets as a Fenton-like catalyst. Chemistry, 2016, 22(27): 9321–9329

[27] Pourghahramani P, Forssberg E. Microstructure characterization of mechanically activated hematite using XRD line broadening. International Journal of Mineral Processing, 2006, 79(2): 106–119

[28] Williamson G K, Hall W H. X-ray line broadening from filed aluminium and wolfram. Acta Metallurgica, 1953, 1(1): 22–31

[29] Lu L, Li L P, Wang X J, Li G S. Understanding of the finite size effects on lattice vibrations and electronic transitions of nano α-Fe₂O₃. Journal of Physical Chemistry B, 2005, 109(36): 17151–17156

[30] Arbain R, Othman M, Palaniandy S. Preparation of iron oxide nanoparticles by mechanical milling. Minerals Engineering, 2011, 24(1): 1–9

[31] Zeng Y, Gu P F, Zhao Z J, Zhang B, Lin Z C, Peng Y X, Li W, Zhao W T, Leng Y C, Tan P H, Yang T, Zhang Z, Song Y, Yang J, Ye Y, Tian K, Hou Y. 2D FeOCl: a highly in-plane anisotropic antiferromagnetic semiconductor synthesized via temperature-oscillation chemical vapor transport. Advanced Materials, 2022, 34(14): 2108847

[32] Fernandez-Izquierdo L, Spera E L, Durán B, Marotti R E, Dalchiele E A, Del Rio R, Hevia S A. CVD growth of hematite thin films for photoelectrochemical water splitting: effect of precursor-substrate distance on their final properties. Molecules, 2023, 28(4): 1954

[33] Tadic M, Trpkov D, Kopanja L, Vojnovic S, Panjan M. Hydrothermal synthesis of hematite (α-Fe₂O₃) nanoparticle forms: synthesis conditions, structure, particle shape analysis, cytotoxicity and magnetic properties. Journal of Alloys and Compounds, 2019, 792: 599–609

[34] Zoltán V, Mária K, Magdolna H. Gas-phase structures of iron trihalides: a computational study of all iron trihalides and an electron diffraction study of iron trichloride. Inorganic Chemistry, 2010, 49(3): 1039–1045

[35] Wang Q C, Lei Y P, Wang Y C, Liu Y, Song C Y, Zeng J, Song Y H, Duan X D, Wang D S, Li Y D. Atomic-scale engineering of chemical-vapor-deposition-grown 2D transition metal dichalcogenides for electrocatalysis. Energy & Environmental Science, 2020, 13(6): 1593–1616

[36] Ji X X, Wang H F, Hu P J. First principles study of Fenton reaction catalyzed by FeOCl: reaction mechanism and location of active site. Rare Metals, 2019, 38(8): 783–792

[37] Pajączkowska A, Majcher K. The chemical vapour transport of Mn₃Fe₂Ge₃O₁₂ garnet. Journal of Materials Science Letters, 1986, 5(4): 487–488

[38] Ferrenti A M, Siegler M A, Gao S Y, Ng N, McQueen T M. ScSI: a new exfoliatable semiconductor. Chemistry of Materials, 2022, 34(12): 5443–5451

[39] Dai Y D, Yu Z, Huang H B, He Y, Shao T, Hsia Y F. Thermal decomposition of iron oxychloride as studied by thermal analysis, X-ray diffraction and Mössbauer spectroscopy. Materials Chemistry and Physics, 2003, 79(1): 94–97

[40] Dai C, Tian X K, Nie Y L, Fu W, Wang J T. Effect of the interaction mode of H₂O₂ over CuMnO₂ surface on •OH generation for efficient degradation of ofloxacin: activity and mechanism. Chemical Engineering Journal, 2023, 451: 138749

[41] Wang Y, Zhong Z, Chen Y, Ng C T, Lin J. Controllable synthesis of Co₃O₄ from nanosize to microsize with large-scale exposure of active crystal planes and their excellent rate capability in supercapacitors based on the crystal plane effect. Nano Research, 2011, 4(7): 695–704

[42] Zhao C, Guo S E, Li Q, Liu J N, Zheng M, Xiao X D, Jiang B J, Fu H G. Supramolecular precursor derived loofah sponge-like Fe₂O_x/C for effective synergistic reaction of Fenton and photocatalysis. Nano Research, 2022, 15(3): 1949–1958

[43] Tan X J, Ding W H, Jiang Z Y, Sun L X, Huang Y X. Reinventing MoS₂ co-catalytic Fenton reaction: oxygen-incorporation mediating surface superoxide radical generation. Nano Research, 2022, 15(3): 1973–1982

[44] Yamashita T, Hayes P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials. Applied Surface Science, 2008, 254(8): 2441–2449

[45] Luo J M, Sun M, Ritt C L, Liu X, Pei Y, Crittenden J C, Elimelech M. Tuning Pb(II) adsorption from aqueous solutions on ultrathin iron oxychloride (FeOCl) nanosheets. Environmental Science & Technology, 2019, 53(4): 2075–2085

[46] Mijangos F, Varona F, Villota N. Changes in solution color during phenol oxidation by Fenton reagent. Environmental Science & Technology, 2006, 40(17): 5538–5543

[47] Feng Y, Han K, Jiang T, Bian Z F, Liang X, Cao X, Li H, Wang Z L. Self-powered electrochemical system by combining Fenton reaction and active chlorine generation for organic contaminant treatment. Nano Research, 2019, 12(11): 2729–2735

[48] Li X Y, Cui Y H, Feng Y J, Xie Z M, Gu J D. Reaction pathways and mechanisms of the electrochemical degradation of phenol on different electrodes. Water Research, 2005, 39(10): 1972–1981

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

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) and the National Natural Science Foundation of China (Grant No. 21876049).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2330-z and is accessible for authorized users.

RIGHTS & PERMISSIONS

2023 Higher Education Press