Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF

Amin Osatiashtiani; Adam F. Lee; Marta Granollers; D. Robert Brown; Luca Olivi; Gabriel Morales; Juan A. Melero; Karen Wilson

doi:10.1021/acscatal.5b00965

Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF

Amin Osatiashtiani, Adam F. Lee, Marta Granollers, D. Robert Brown, Luca Olivi, Gabriel Morales, Juan A. Melero, Karen Wilson^*

^*Corresponding author for this work

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

Abstract

The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Brönsted and Lewis acidity, with the Brönsted/Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Brönsted/Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO₂/SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a 3-fold enhancement in 5-HMF productivity over nonporous SZ counterparts. The coexistence of accessible solid basic/Lewis acid and Brönsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively formed fructose to the desired 5-HMF platform chemical.

Original language	English
Pages (from-to)	4345-4352
Number of pages	8
Journal	ACS Catalysis
Volume	5
Issue number	7
DOIs	https://doi.org/10.1021/acscatal.5b00965
Publication status	Published - 17 Jun 2015

Bibliographical note

This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Funding: European Union Seventh Framework Programme (FP7/2007-2013) Grant Agreement No. 604307; EPSRC (EP/K014676/1; EP/G007594/4); Royal Society (IF100206); Ministerio de Ciencia e Innovación of Spain (CTQ2011-28216); and Regional Government of Madrid (S2013-MAE-288)

Supporting information avaialble online.

Keywords

SBA-15
solid base
hydrothermal stability
5-HMF
solid acid
sulfated zirconia

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10.1021/acscatal.5b00965

Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF
This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Final published version, 1.37 MB

Cite this

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title = "Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF",

abstract = "The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Br{\"o}nsted and Lewis acidity, with the Br{\"o}nsted/Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Br{\"o}nsted/Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO2/SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a 3-fold enhancement in 5-HMF productivity over nonporous SZ counterparts. The coexistence of accessible solid basic/Lewis acid and Br{\"o}nsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively formed fructose to the desired 5-HMF platform chemical.",

keywords = "SBA-15, solid base, hydrothermal stability, 5-HMF, solid acid, sulfated zirconia",

author = "Amin Osatiashtiani and Lee, {Adam F.} and Marta Granollers and Brown, {D. Robert} and Luca Olivi and Gabriel Morales and Melero, {Juan A.} and Karen Wilson",

note = "This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Funding: European Union Seventh Framework Programme (FP7/2007-2013) Grant Agreement No. 604307; EPSRC (EP/K014676/1; EP/G007594/4); Royal Society (IF100206); Ministerio de Ciencia e Innovaci{\'o}n of Spain (CTQ2011-28216); and Regional Government of Madrid (S2013-MAE-288) Supporting information avaialble online.",

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doi = "10.1021/acscatal.5b00965",

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AU - Osatiashtiani, Amin

AU - Lee, Adam F.

AU - Granollers, Marta

AU - Brown, D. Robert

AU - Olivi, Luca

AU - Morales, Gabriel

AU - Melero, Juan A.

AU - Wilson, Karen

N1 - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Funding: European Union Seventh Framework Programme (FP7/2007-2013) Grant Agreement No. 604307; EPSRC (EP/K014676/1; EP/G007594/4); Royal Society (IF100206); Ministerio de Ciencia e Innovación of Spain (CTQ2011-28216); and Regional Government of Madrid (S2013-MAE-288) Supporting information avaialble online.

PY - 2015/6/17

Y1 - 2015/6/17

N2 - The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Brönsted and Lewis acidity, with the Brönsted/Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Brönsted/Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO2/SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a 3-fold enhancement in 5-HMF productivity over nonporous SZ counterparts. The coexistence of accessible solid basic/Lewis acid and Brönsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively formed fructose to the desired 5-HMF platform chemical.

AB - The grafting and sulfation of zirconia conformal monolayers on SBA-15 to create mesoporous catalysts of tunable solid acid/base character is reported. Conformal zirconia and sulfated zirconia (SZ) materials exhibit both Brönsted and Lewis acidity, with the Brönsted/Lewis acid ratio increasing with film thickness and sulfate content. Grafted zirconia films also exhibit amphoteric character, whose Brönsted/Lewis acid site ratio increases with sulfate loading at the expense of base sites. Bilayer ZrO2/SBA-15 affords an ordered mesoporous material with a high acid site loading upon sulfation and excellent hydrothermal stability. Catalytic performance of SZ/SBA-15 was explored in the aqueous phase conversion of glucose to 5-HMF, delivering a 3-fold enhancement in 5-HMF productivity over nonporous SZ counterparts. The coexistence of accessible solid basic/Lewis acid and Brönsted acid sites in grafted SZ/SBA-15 promotes the respective isomerization of glucose to fructose and dehydration of reactively formed fructose to the desired 5-HMF platform chemical.

KW - SBA-15

KW - solid base

KW - hydrothermal stability

KW - 5-HMF

KW - solid acid

KW - sulfated zirconia

UR - http://pubs.acs.org/doi/abs/10.1021/acscatal.5b00965

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U2 - 10.1021/acscatal.5b00965

DO - 10.1021/acscatal.5b00965

M3 - Article

SN - 2155-5435

VL - 5

SP - 4345

EP - 4352

JO - ACS Catalysis

JF - ACS Catalysis

IS - 7

ER -

Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF

Abstract

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