Support enhanced α-pinene isomerization over HPW/SBA-15

Lucia Frattini; Mark A. Isaacs; Christopher M.A. Parlett; Karen Wilson; Georgios Kyriakou; Adam F. Lee

doi:10.1016/j.apcatb.2016.06.064

Support enhanced α-pinene isomerization over HPW/SBA-15

Lucia Frattini, Mark A. Isaacs, Christopher M.A. Parlett, Karen Wilson, Georgios Kyriakou, Adam F. Lee^*

^*Corresponding author for this work

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

Abstract

A family of mesoporous SBA-15 supported H₃PW₁₂O₄₀ (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N₂ porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g⁻¹) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.

Original language	English
Pages (from-to)	10-18
Number of pages	9
Journal	Applied Catalysis B: Environmental
Volume	200
Early online date	27 Jun 2016
DOIs	https://doi.org/10.1016/j.apcatb.2016.06.064
Publication status	Published - Jan 2017

Bibliographical note

© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

Funding: EPSRC (EP/K000616/2; EP/K014749/1 and EP/M005186/1), Royal Society, and British Council under the Global Innovation Initiative for the GB3-net project.

Supplementary data available on the journal website.

Keywords

heteropolyacid
phosphotungstic acid
SBA-15
α-pinene

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10.1016/j.apcatb.2016.06.064Licence: CC BY 3.0

Support enhanced alpha-pinene isomerization
© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)
Final published version, 3.34 MBLicence: CC BY 3.0

Cite this

@article{70ceae114ec44d458da337463a795cb1,

title = "Support enhanced α-pinene isomerization over HPW/SBA-15",

abstract = "A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.",

keywords = "heteropolyacid, phosphotungstic acid, SBA-15, α-pinene",

author = "Lucia Frattini and Isaacs, {Mark A.} and Parlett, {Christopher M.A.} and Karen Wilson and Georgios Kyriakou and Lee, {Adam F.}",

note = "{\textcopyright} 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) Funding: EPSRC (EP/K000616/2; EP/K014749/1 and EP/M005186/1), Royal Society, and British Council under the Global Innovation Initiative for the GB3-net project. Supplementary data available on the journal website.",

year = "2017",

month = jan,

doi = "10.1016/j.apcatb.2016.06.064",

language = "English",

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AU - Frattini, Lucia

AU - Isaacs, Mark A.

AU - Parlett, Christopher M.A.

AU - Wilson, Karen

AU - Kyriakou, Georgios

AU - Lee, Adam F.

N1 - © 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) Funding: EPSRC (EP/K000616/2; EP/K014749/1 and EP/M005186/1), Royal Society, and British Council under the Global Innovation Initiative for the GB3-net project. Supplementary data available on the journal website.

PY - 2017/1

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N2 - A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.

AB - A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.

KW - heteropolyacid

KW - phosphotungstic acid

KW - SBA-15

KW - α-pinene

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JO - Applied Catalysis B: Environmental

JF - Applied Catalysis B: Environmental

ER -

Support enhanced α-pinene isomerization over HPW/SBA-15

Abstract

Bibliographical note

Keywords

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