Open-framework iron phosphates: Syntheses, structures, sorption studies and oxidation catalysis

Khalid Abu-Shandi; Heiner Winkler; Biao Wu; Christoph Janiak

doi:10.1039/b303498d

Open-framework iron phosphates: Syntheses, structures, sorption studies and oxidation catalysis

Khalid Abu-Shandi, Heiner Winkler, Biao Wu, Christoph Janiak^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

33 Citations (Scopus)

Abstract

The iron phosphates [C₄H₁₂N₂][Fe ^II(H₂O)₆](HPO₄)₂ (1), ³∞{[NH₄][Fe^III ₂(OH)(PO ₄)₂(H₂O)]•H₂O} (2) and ³∞{[C₄H₁₂N₂][Fe^III ₃(PO₄)₃(HPO₄)(H₂O)] •̃ 0.25H₂O}, (3) were synthesized by hydrothermal methods and their single-crystal X-ray structures were determined. While compound 1 is only an extended hydrogen bonded network of its three ionic building blocks, compounds 2 and 3 are threedimensional open-framework materials albeit of different porosity. The structure of 2 corresponds to the mineral sphenicidite. The iron building blocks in 3 are pairs of distorted edge-sharing {FeO ₆} octahedra and a five-coordinated iron atom, {FeO₅}, with a mostly trigonal-bipyramidal polyhedron. The oxidation-state assignment of 2 was backed by ⁵⁷Fe Mössbauer spectroscopy. Thermogravimetric analysis (TGA) of 2 and 3 shows clearly separated steps of weight loss due to the loss of water of crystallization, aqua ligand and amine template molecules. X-ray powder diffractometry proved that the empty host-frameworks were still intact after heating to 215°C. The porous empty frameworks of 2 and 3 could be employed as sorbents towards alkanes, alcohols, chlorinated halocarbons, amines and ethers. The larger-porous framework of 3 (but not that of 2) was found to be a catalyst for the highly regioselective oxidation of n-pentane to 3-pentanol with air at 15 bar and 100°C.

Original language	English
Pages (from-to)	180-189
Number of pages	10
Journal	CrystEngComm
Volume	5
DOIs	https://doi.org/10.1039/b303498d
Publication status	Published - 23 May 2003
Externally published	Yes

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title = "Open-framework iron phosphates: Syntheses, structures, sorption studies and oxidation catalysis",

abstract = "The iron phosphates [C4H12N2][Fe II(H2O)6](HPO4)2 (1), 3∞{[NH4][FeIII 2(OH)(PO 4)2(H2O)]•H2O} (2) and 3∞{[C4H12N2][FeIII 3(PO4)3(HPO4)(H2O)] {\~•} 0.25H2O}, (3) were synthesized by hydrothermal methods and their single-crystal X-ray structures were determined. While compound 1 is only an extended hydrogen bonded network of its three ionic building blocks, compounds 2 and 3 are threedimensional open-framework materials albeit of different porosity. The structure of 2 corresponds to the mineral sphenicidite. The iron building blocks in 3 are pairs of distorted edge-sharing {FeO 6} octahedra and a five-coordinated iron atom, {FeO5}, with a mostly trigonal-bipyramidal polyhedron. The oxidation-state assignment of 2 was backed by 57Fe M{\"o}ssbauer spectroscopy. Thermogravimetric analysis (TGA) of 2 and 3 shows clearly separated steps of weight loss due to the loss of water of crystallization, aqua ligand and amine template molecules. X-ray powder diffractometry proved that the empty host-frameworks were still intact after heating to 215°C. The porous empty frameworks of 2 and 3 could be employed as sorbents towards alkanes, alcohols, chlorinated halocarbons, amines and ethers. The larger-porous framework of 3 (but not that of 2) was found to be a catalyst for the highly regioselective oxidation of n-pentane to 3-pentanol with air at 15 bar and 100°C.",

author = "Khalid Abu-Shandi and Heiner Winkler and Biao Wu and Christoph Janiak",

year = "2003",

month = may,

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doi = "10.1039/b303498d",

language = "English",

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journal = "CrystEngComm",

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T1 - Open-framework iron phosphates

T2 - Syntheses, structures, sorption studies and oxidation catalysis

AU - Abu-Shandi, Khalid

AU - Winkler, Heiner

AU - Wu, Biao

AU - Janiak, Christoph

PY - 2003/5/23

Y1 - 2003/5/23

N2 - The iron phosphates [C4H12N2][Fe II(H2O)6](HPO4)2 (1), 3∞{[NH4][FeIII 2(OH)(PO 4)2(H2O)]•H2O} (2) and 3∞{[C4H12N2][FeIII 3(PO4)3(HPO4)(H2O)] •̃ 0.25H2O}, (3) were synthesized by hydrothermal methods and their single-crystal X-ray structures were determined. While compound 1 is only an extended hydrogen bonded network of its three ionic building blocks, compounds 2 and 3 are threedimensional open-framework materials albeit of different porosity. The structure of 2 corresponds to the mineral sphenicidite. The iron building blocks in 3 are pairs of distorted edge-sharing {FeO 6} octahedra and a five-coordinated iron atom, {FeO5}, with a mostly trigonal-bipyramidal polyhedron. The oxidation-state assignment of 2 was backed by 57Fe Mössbauer spectroscopy. Thermogravimetric analysis (TGA) of 2 and 3 shows clearly separated steps of weight loss due to the loss of water of crystallization, aqua ligand and amine template molecules. X-ray powder diffractometry proved that the empty host-frameworks were still intact after heating to 215°C. The porous empty frameworks of 2 and 3 could be employed as sorbents towards alkanes, alcohols, chlorinated halocarbons, amines and ethers. The larger-porous framework of 3 (but not that of 2) was found to be a catalyst for the highly regioselective oxidation of n-pentane to 3-pentanol with air at 15 bar and 100°C.

AB - The iron phosphates [C4H12N2][Fe II(H2O)6](HPO4)2 (1), 3∞{[NH4][FeIII 2(OH)(PO 4)2(H2O)]•H2O} (2) and 3∞{[C4H12N2][FeIII 3(PO4)3(HPO4)(H2O)] •̃ 0.25H2O}, (3) were synthesized by hydrothermal methods and their single-crystal X-ray structures were determined. While compound 1 is only an extended hydrogen bonded network of its three ionic building blocks, compounds 2 and 3 are threedimensional open-framework materials albeit of different porosity. The structure of 2 corresponds to the mineral sphenicidite. The iron building blocks in 3 are pairs of distorted edge-sharing {FeO 6} octahedra and a five-coordinated iron atom, {FeO5}, with a mostly trigonal-bipyramidal polyhedron. The oxidation-state assignment of 2 was backed by 57Fe Mössbauer spectroscopy. Thermogravimetric analysis (TGA) of 2 and 3 shows clearly separated steps of weight loss due to the loss of water of crystallization, aqua ligand and amine template molecules. X-ray powder diffractometry proved that the empty host-frameworks were still intact after heating to 215°C. The porous empty frameworks of 2 and 3 could be employed as sorbents towards alkanes, alcohols, chlorinated halocarbons, amines and ethers. The larger-porous framework of 3 (but not that of 2) was found to be a catalyst for the highly regioselective oxidation of n-pentane to 3-pentanol with air at 15 bar and 100°C.

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U2 - 10.1039/b303498d

DO - 10.1039/b303498d

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SN - 1466-8033

VL - 5

SP - 180

EP - 189

JO - CrystEngComm

JF - CrystEngComm

ER -

Open-framework iron phosphates: Syntheses, structures, sorption studies and oxidation catalysis

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