Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation

Laura Mitchell; Patrick Williamson; Barbora Ehrlichova; Amanda Elizabeth Anderson; Valerie Ruth Seymour; Sharon Elizabeth  Ashbrook; Nadia Acerbi; Luke Daniels; Richard Walton; Matthew L. Clarke; Paul Anthony Wright

doi:10.1002/chem.201404377

Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation

Laura Mitchell, Patrick Williamson, Barbora Ehrlichova, Amanda Elizabeth Anderson, Valerie Ruth Seymour, Sharon Elizabeth Ashbrook, Nadia Acerbi, Luke Daniels, Richard Walton, Matthew L. Clarke^*, Paul Anthony Wright^*

^*Corresponding author for this work

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

Abstract

The trivalent metal cations Al³⁺, Cr³⁺, and Fe³⁺ were each introduced, together with Sc³⁺, into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe₂O₃ nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel–Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe₂O₃ nanoparticles were also active Lewis acid species, although less active than Sc³⁺ in trimer sites. The incorporation of Fe³⁺ into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc³⁺ and Fe³⁺. A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.

Original language	English
Pages (from-to)	17185-17197
Number of pages	14
Journal	Chemistry - A European Journal
Volume	20
Issue number	51
Early online date	27 Oct 2014
DOIs	https://doi.org/10.1002/chem.201404377
Publication status	Published - 5 Dec 2014

Keywords

Bifunctional catalysts
Heterogeneous catalysis
Iron
Scandium
Tandem catalysis

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10.1002/chem.201404377

MIL-100-ScFe-160914
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at http://dx.doi.org/10.1002/chem.201404377
Accepted author manuscript, 1.79 MB

Cite this

Mitchell, L., Williamson, P., Ehrlichova, B., Anderson, A. E., Seymour, V. R., Ashbrook, S. E., Acerbi, N., Daniels, L., Walton, R., Clarke, M. L., & Wright, P. A. (2014). Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation. Chemistry - A European Journal, 20(51), 17185-17197. https://doi.org/10.1002/chem.201404377

@article{d93818fbfb1543fb8aa70108c9666c87,

title = "Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation",

abstract = "The trivalent metal cations Al3+, Cr3+, and Fe3+ were each introduced, together with Sc3+, into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel–Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2O3 nanoparticles were also active Lewis acid species, although less active than Sc3+ in trimer sites. The incorporation of Fe3+ into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc3+ and Fe3+. A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.",

keywords = "Bifunctional catalysts, Heterogeneous catalysis, Iron, Scandium, Tandem catalysis",

author = "Laura Mitchell and Patrick Williamson and Barbora Ehrlichova and Anderson, {Amanda Elizabeth} and Seymour, {Valerie Ruth} and Ashbrook, {Sharon Elizabeth} and Nadia Acerbi and Luke Daniels and Richard Walton and Clarke, {Matthew L.} and Wright, {Paul Anthony}",

note = "The authors thank Johnson Matthey and the EPSRC for an Industrial CASE award to L.M. We gratefully acknowledge the IAESTE UK for a scholarship to B.E. They also thank the Leverhulme Trust (F/00 268/BJ), EPSRC (EP/J501542/1), and the EaStCHEM Research Computing Facility.",

year = "2014",

month = dec,

day = "5",

doi = "10.1002/chem.201404377",

language = "English",

volume = "20",

pages = "17185--17197",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley & Sons, Ltd",

number = "51",

}

Mitchell, L, Williamson, P, Ehrlichova, B, Anderson, AE, Seymour, VR, Ashbrook, SE, Acerbi, N, Daniels, L, Walton, R, Clarke, ML & Wright, PA 2014, 'Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation', Chemistry - A European Journal, vol. 20, no. 51, pp. 17185-17197. https://doi.org/10.1002/chem.201404377

TY - JOUR

T1 - Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation

AU - Mitchell, Laura

AU - Williamson, Patrick

AU - Ehrlichova, Barbora

AU - Anderson, Amanda Elizabeth

AU - Seymour, Valerie Ruth

AU - Ashbrook, Sharon Elizabeth

AU - Acerbi, Nadia

AU - Daniels, Luke

AU - Walton, Richard

AU - Clarke, Matthew L.

AU - Wright, Paul Anthony

N1 - The authors thank Johnson Matthey and the EPSRC for an Industrial CASE award to L.M. We gratefully acknowledge the IAESTE UK for a scholarship to B.E. They also thank the Leverhulme Trust (F/00 268/BJ), EPSRC (EP/J501542/1), and the EaStCHEM Research Computing Facility.

PY - 2014/12/5

Y1 - 2014/12/5

N2 - The trivalent metal cations Al3+, Cr3+, and Fe3+ were each introduced, together with Sc3+, into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel–Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2O3 nanoparticles were also active Lewis acid species, although less active than Sc3+ in trimer sites. The incorporation of Fe3+ into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc3+ and Fe3+. A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.

AB - The trivalent metal cations Al3+, Cr3+, and Fe3+ were each introduced, together with Sc3+, into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel–Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2O3 nanoparticles were also active Lewis acid species, although less active than Sc3+ in trimer sites. The incorporation of Fe3+ into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc3+ and Fe3+. A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.

KW - Bifunctional catalysts

KW - Heterogeneous catalysis

KW - Iron

KW - Scandium

KW - Tandem catalysis

UR - http://onlinelibrary.wiley.com/doi/10.1002/chem.201404377/suppinfo

U2 - 10.1002/chem.201404377

DO - 10.1002/chem.201404377

M3 - Article

SN - 0947-6539

VL - 20

SP - 17185

EP - 17197

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 51

ER -

Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation

Abstract

Keywords

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EPSRC Strategic partner projects-applica: Expanding the capability for variable temperature solid-state NMR in St Andrews

EPSRC Strategic partner projects applica: An active, provenance-preserving scientific data store

170 NMR of microporous solids: 170 NMR of microporous solids

Matt Clarke

Paul Anthony Wright

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Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation

Abstract

Keywords

Access to Document

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Projects

EPSRC Strategic partner projects-applica: Expanding the capability for variable temperature solid-state NMR in St Andrews

EPSRC Strategic partner projects applica: An active, provenance-preserving scientific data store

170 NMR of microporous solids: 170 NMR of microporous solids

Profiles

Matt Clarke

Paul Anthony Wright

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