Phase-controlled synthesis of iron phosphates: Via phosphation of β-FeOOH nanorods

Ronghe Lin, Amol P. Amrute, Frank Krumeich, K. Lázár, Roland Hauert, Maxim Yulikov, Javier Pérez-Ramírez

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Iron phosphates comprise an important class of materials with a wide range of applications. We have designed novel routes for the controlled synthesis of iron phosphate dihydrates of varying crystallographic phases (monoclinic and orthorhombic) and morphologies. Our approach comprises the phosphation of β-FeOOH nanorods with aqueous phosphoric acid solutions. Through a systematic parametric study coupled to an array of characterisation techniques, including XRD, TEM, HAADF-STEM, AAS, N2 sorption, TGA-MS, FTIR, UV-Vis, XPS, EXAFS, EPR, and 57Fe Mössbauer spectroscopy, we unravel the complex synthesis chemistry on both the macroscopic and microscopic levels. It is found that the formation of iron phosphates occurs exclusively under acidic conditions and in general involves the dissolution of β-FeOOH which, upon reaction with H3PO4, precipitates as FePO4·2H2O. The pH of the treatment solution determines the crystallographic phase of the resulting product by regulating the rate of β-FeOOH dissolution and of the precipitation of the iron phosphates, while the treatment time is decisive for the preservation of the morphology. The formation of the monoclinic phase entails a fast iron dissolution and subsequent precipitation in the solution. The generation of the orthorhombic analogue involves an interfacial reaction between H3PO4 and β-FeOOH, forming an amorphous layer of iron phosphate, which crystallises into a pure phase with increasing treatment time. The thermal transformation of hydrated to anhydrous iron phosphates is dependent on the phase and morphology of the precursors. The rod shape of iron-rich orthorhombic FePO4·2H2O can be preserved even after annealing at 923 K, with the formation of mesopores. These novel nanostructures may widen the applications of iron phosphates and the routes developed herein can be anticipated to guide the fabrication of other metal phosphates.

Original languageEnglish
Pages (from-to)3174-3185
Number of pages12
JournalCrystEngComm
Volume18
Issue number18
DOIs
Publication statusPublished - 2016

Fingerprint

Nanorods
nanorods
phosphates
Phosphates
Iron
iron
synthesis
dissolving
Dissolution
synthesis (chemistry)
routes
phosphoric acid
Phosphoric acid
Surface chemistry
sorption
Paramagnetic resonance
Sorption
Precipitates
precipitates
Nanostructures

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Lin, R., Amrute, A. P., Krumeich, F., Lázár, K., Hauert, R., Yulikov, M., & Pérez-Ramírez, J. (2016). Phase-controlled synthesis of iron phosphates: Via phosphation of β-FeOOH nanorods. CrystEngComm, 18(18), 3174-3185. https://doi.org/10.1039/c6ce00501b

Phase-controlled synthesis of iron phosphates : Via phosphation of β-FeOOH nanorods. / Lin, Ronghe; Amrute, Amol P.; Krumeich, Frank; Lázár, K.; Hauert, Roland; Yulikov, Maxim; Pérez-Ramírez, Javier.

In: CrystEngComm, Vol. 18, No. 18, 2016, p. 3174-3185.

Research output: Contribution to journalArticle

Lin, R, Amrute, AP, Krumeich, F, Lázár, K, Hauert, R, Yulikov, M & Pérez-Ramírez, J 2016, 'Phase-controlled synthesis of iron phosphates: Via phosphation of β-FeOOH nanorods', CrystEngComm, vol. 18, no. 18, pp. 3174-3185. https://doi.org/10.1039/c6ce00501b
Lin, Ronghe ; Amrute, Amol P. ; Krumeich, Frank ; Lázár, K. ; Hauert, Roland ; Yulikov, Maxim ; Pérez-Ramírez, Javier. / Phase-controlled synthesis of iron phosphates : Via phosphation of β-FeOOH nanorods. In: CrystEngComm. 2016 ; Vol. 18, No. 18. pp. 3174-3185.
@article{dc5124da61aa47619d94640f8dc29375,
title = "Phase-controlled synthesis of iron phosphates: Via phosphation of β-FeOOH nanorods",
abstract = "Iron phosphates comprise an important class of materials with a wide range of applications. We have designed novel routes for the controlled synthesis of iron phosphate dihydrates of varying crystallographic phases (monoclinic and orthorhombic) and morphologies. Our approach comprises the phosphation of β-FeOOH nanorods with aqueous phosphoric acid solutions. Through a systematic parametric study coupled to an array of characterisation techniques, including XRD, TEM, HAADF-STEM, AAS, N2 sorption, TGA-MS, FTIR, UV-Vis, XPS, EXAFS, EPR, and 57Fe M{\"o}ssbauer spectroscopy, we unravel the complex synthesis chemistry on both the macroscopic and microscopic levels. It is found that the formation of iron phosphates occurs exclusively under acidic conditions and in general involves the dissolution of β-FeOOH which, upon reaction with H3PO4, precipitates as FePO4·2H2O. The pH of the treatment solution determines the crystallographic phase of the resulting product by regulating the rate of β-FeOOH dissolution and of the precipitation of the iron phosphates, while the treatment time is decisive for the preservation of the morphology. The formation of the monoclinic phase entails a fast iron dissolution and subsequent precipitation in the solution. The generation of the orthorhombic analogue involves an interfacial reaction between H3PO4 and β-FeOOH, forming an amorphous layer of iron phosphate, which crystallises into a pure phase with increasing treatment time. The thermal transformation of hydrated to anhydrous iron phosphates is dependent on the phase and morphology of the precursors. The rod shape of iron-rich orthorhombic FePO4·2H2O can be preserved even after annealing at 923 K, with the formation of mesopores. These novel nanostructures may widen the applications of iron phosphates and the routes developed herein can be anticipated to guide the fabrication of other metal phosphates.",
author = "Ronghe Lin and Amrute, {Amol P.} and Frank Krumeich and K. L{\'a}z{\'a}r and Roland Hauert and Maxim Yulikov and Javier P{\'e}rez-Ram{\'i}rez",
year = "2016",
doi = "10.1039/c6ce00501b",
language = "English",
volume = "18",
pages = "3174--3185",
journal = "CrystEngComm",
issn = "1466-8033",
publisher = "Royal Society of Chemistry",
number = "18",

}

TY - JOUR

T1 - Phase-controlled synthesis of iron phosphates

T2 - Via phosphation of β-FeOOH nanorods

AU - Lin, Ronghe

AU - Amrute, Amol P.

AU - Krumeich, Frank

AU - Lázár, K.

AU - Hauert, Roland

AU - Yulikov, Maxim

AU - Pérez-Ramírez, Javier

PY - 2016

Y1 - 2016

N2 - Iron phosphates comprise an important class of materials with a wide range of applications. We have designed novel routes for the controlled synthesis of iron phosphate dihydrates of varying crystallographic phases (monoclinic and orthorhombic) and morphologies. Our approach comprises the phosphation of β-FeOOH nanorods with aqueous phosphoric acid solutions. Through a systematic parametric study coupled to an array of characterisation techniques, including XRD, TEM, HAADF-STEM, AAS, N2 sorption, TGA-MS, FTIR, UV-Vis, XPS, EXAFS, EPR, and 57Fe Mössbauer spectroscopy, we unravel the complex synthesis chemistry on both the macroscopic and microscopic levels. It is found that the formation of iron phosphates occurs exclusively under acidic conditions and in general involves the dissolution of β-FeOOH which, upon reaction with H3PO4, precipitates as FePO4·2H2O. The pH of the treatment solution determines the crystallographic phase of the resulting product by regulating the rate of β-FeOOH dissolution and of the precipitation of the iron phosphates, while the treatment time is decisive for the preservation of the morphology. The formation of the monoclinic phase entails a fast iron dissolution and subsequent precipitation in the solution. The generation of the orthorhombic analogue involves an interfacial reaction between H3PO4 and β-FeOOH, forming an amorphous layer of iron phosphate, which crystallises into a pure phase with increasing treatment time. The thermal transformation of hydrated to anhydrous iron phosphates is dependent on the phase and morphology of the precursors. The rod shape of iron-rich orthorhombic FePO4·2H2O can be preserved even after annealing at 923 K, with the formation of mesopores. These novel nanostructures may widen the applications of iron phosphates and the routes developed herein can be anticipated to guide the fabrication of other metal phosphates.

AB - Iron phosphates comprise an important class of materials with a wide range of applications. We have designed novel routes for the controlled synthesis of iron phosphate dihydrates of varying crystallographic phases (monoclinic and orthorhombic) and morphologies. Our approach comprises the phosphation of β-FeOOH nanorods with aqueous phosphoric acid solutions. Through a systematic parametric study coupled to an array of characterisation techniques, including XRD, TEM, HAADF-STEM, AAS, N2 sorption, TGA-MS, FTIR, UV-Vis, XPS, EXAFS, EPR, and 57Fe Mössbauer spectroscopy, we unravel the complex synthesis chemistry on both the macroscopic and microscopic levels. It is found that the formation of iron phosphates occurs exclusively under acidic conditions and in general involves the dissolution of β-FeOOH which, upon reaction with H3PO4, precipitates as FePO4·2H2O. The pH of the treatment solution determines the crystallographic phase of the resulting product by regulating the rate of β-FeOOH dissolution and of the precipitation of the iron phosphates, while the treatment time is decisive for the preservation of the morphology. The formation of the monoclinic phase entails a fast iron dissolution and subsequent precipitation in the solution. The generation of the orthorhombic analogue involves an interfacial reaction between H3PO4 and β-FeOOH, forming an amorphous layer of iron phosphate, which crystallises into a pure phase with increasing treatment time. The thermal transformation of hydrated to anhydrous iron phosphates is dependent on the phase and morphology of the precursors. The rod shape of iron-rich orthorhombic FePO4·2H2O can be preserved even after annealing at 923 K, with the formation of mesopores. These novel nanostructures may widen the applications of iron phosphates and the routes developed herein can be anticipated to guide the fabrication of other metal phosphates.

UR - http://www.scopus.com/inward/record.url?scp=84967327612&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84967327612&partnerID=8YFLogxK

U2 - 10.1039/c6ce00501b

DO - 10.1039/c6ce00501b

M3 - Article

AN - SCOPUS:84967327612

VL - 18

SP - 3174

EP - 3185

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 18

ER -