Staff View: Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals

Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals

Catalytic conversion of glycerol into value-added chemicals, particularly acrolein via acid-catalyzed dehydration route has received much attention due to the potential uses of acrolein. This work reports the synthesis of various alkaline metal substituted phosphotungstic acid (H3PW12O40, HPW) catal...

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Main Authors:	Hamid, Sharifah Bee Abd, Daud, N.A., Suppiah, Durga Devi, Yehya, W.A., Sudarsanam, P., Bhargava, S.K.
Format:	Article
Language:	English
Published:	Elsevier 2016
Subjects:	QD Chemistry
Online Access:	http://eprints.um.edu.my/17419/1/Catalytic_dehydration_of_glycerol_to_acrolein_over_M.pdf http://eprints.um.edu.my/17419/ http://www.sciencedirect.com/science/article/pii/S0277538716303862 https://doi.org/10.1016/j.poly.2016.08.027
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institution	Universiti Malaya
building	UM Library
collection	Institutional Repository
continent	Asia
country	Malaysia
content_provider	Universiti Malaya
content_source	UM Research Repository
url_provider	http://eprints.um.edu.my/
language	English
topic	QD Chemistry
spellingShingle	QD Chemistry Hamid, Sharifah Bee Abd Daud, N.A. Suppiah, Durga Devi Yehya, W.A. Sudarsanam, P. Bhargava, S.K. Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals
description	Catalytic conversion of glycerol into value-added chemicals, particularly acrolein via acid-catalyzed dehydration route has received much attention due to the potential uses of acrolein. This work reports the synthesis of various alkaline metal substituted phosphotungstic acid (H3PW12O40, HPW) catalysts, namely M2.5H0.5PW12O40 (M = Cs, Rb and K) using a controlled precipitation method. A systematic structural, morphology, and chemical characterization were conducted using various analytical techniques. XRD studies revealed that the incorporation of alkaline metals in H3PW12O40 leads to decreased crystallite size and enhanced lattice strain. N2 adsorption–desorption studies show that the specific surface area of H3PW12O40 is significantly improved from 5 to 82 (K2.5H0.5PW12O40), 103 (Rb2.5H0.5PW12O40), and 94 m2/g (Cs2.5H0.5PW12O40). XRD, Raman, and FT-IR studies confirm the Keggin structure of all the alkaline metal substituted HPW catalysts. The acidity strengths estimated by NH3-TPD analysis were obtained in the following order: H3PW (2654.91 μmole/g) > K2.5H0.5PW (1060.10 μmole/g) > Rb2.5H0.5PW (762.08 μmole/g) > Cs2.5H0.5.5PW (461.81 μmole/g). Although alkaline metal substituted H3PW12O40 catalysts exhibit higher specific surface area and smaller crystallite size compared to parent H3PW12O40 low glycerol conversions were found for substituted H3PW12O40 catalysts. As well, the parent H3PW12O40 catalyst shows an excellent acrolein selectivity (95%) which is much higher than that of Cs2.5H0.5.5PW (81.9%) and very close to the selectivities obtained over Rb2.5H0.5PW (95.1%) and K2.5H0.5.5PW (95.6%) catalysts. The catalytic performance of H3PW12O40 and M2.5H0.5PW12O40 materials is directly proportional to their acidic strengths, indicating that the catalyst acidity is a key factor for achieving better results in glycerol dehydration. Graphical Abstract Catalytic conversion of glycerol into value-added chemicals, particularly acrolein via acid-catalyzed dehydration route has received much attention due to the potential uses of acrolein. This work reports the synthesis of various alkaline metal substituted phosphotungstic acid (H3PW12O40, HPW) catalysts, namely M2.5H0.5PW12O40 (M = Cs, Rb and K) using a controlled precipitation method. A systematic structural, morphology, and chemical characterization were conducted using various analytical techniques. XRD studies revealed that the incorporation of alkaline metals in H3PW12O40 leads to decreased crystallite size and enhanced lattice strain. N2 adsorption–desorption studies show that the specific surface area of H3PW12O40 is significantly improved from 5 to 82 (K2.5H0.5PW12O40), 103 (Rb2.5H0.5PW12O40), and 94 m2/g (Cs2.5H0.5PW12O40). XRD, Raman, and FT-IR studies confirm the Keggin structure of all the alkaline metal substituted HPW catalysts. The acidity strengths estimated by NH3-TPD analysis were obtained in the following order: H3PW (2654.91 μmole/g) > K2.5H0.5PW (1060.10 μmole/g) > Rb2.5H0.5PW (762.08 μmole/g) > Cs2.5H0.5.5PW (461.81 μmole/g). Although alkaline metal substituted H3PW12O40 catalysts exhibit higher specific surface area and smaller crystallite size compared to parent H3PW12O40 low glycerol conversions were found for substituted H3PW12O40 catalysts. As well, the parent H3PW12O40 catalyst shows an excellent acrolein selectivity (95%) which is much higher than that of Cs2.5H0.5.5PW (81.9%) and very close to the selectivities obtained over Rb2.5H0.5PW (95.1%) and K2.5H0.5.5PW (95.6%) catalysts. The catalytic performance of H3PW12O40 and M2.5H0.5PW12O40 materials is directly proportional to their acidic strengths, indicating that the catalyst acidity is a key factor for achieving better results in glycerol dehydration.
format	Article
author	Hamid, Sharifah Bee Abd Daud, N.A. Suppiah, Durga Devi Yehya, W.A. Sudarsanam, P. Bhargava, S.K.
author_facet	Hamid, Sharifah Bee Abd Daud, N.A. Suppiah, Durga Devi Yehya, W.A. Sudarsanam, P. Bhargava, S.K.
author_sort	Hamid, Sharifah Bee Abd
title	Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals
title_short	Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals
title_full	Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals
title_fullStr	Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals
title_full_unstemmed	Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals
title_sort	catalytic dehydration of glycerol to acrolein over m2.5h0.5pw12o40 (m = cs, rb and k) phosphotungstic acids: effect of substituted alkali metals
publisher	Elsevier
publishDate	2016
url	http://eprints.um.edu.my/17419/1/Catalytic_dehydration_of_glycerol_to_acrolein_over_M.pdf http://eprints.um.edu.my/17419/ http://www.sciencedirect.com/science/article/pii/S0277538716303862 https://doi.org/10.1016/j.poly.2016.08.027
_version_	1643690411654381568
spelling	my.um.eprints.174192018-10-19T04:13:06Z http://eprints.um.edu.my/17419/ Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals Hamid, Sharifah Bee Abd Daud, N.A. Suppiah, Durga Devi Yehya, W.A. Sudarsanam, P. Bhargava, S.K. QD Chemistry Catalytic conversion of glycerol into value-added chemicals, particularly acrolein via acid-catalyzed dehydration route has received much attention due to the potential uses of acrolein. This work reports the synthesis of various alkaline metal substituted phosphotungstic acid (H3PW12O40, HPW) catalysts, namely M2.5H0.5PW12O40 (M = Cs, Rb and K) using a controlled precipitation method. A systematic structural, morphology, and chemical characterization were conducted using various analytical techniques. XRD studies revealed that the incorporation of alkaline metals in H3PW12O40 leads to decreased crystallite size and enhanced lattice strain. N2 adsorption–desorption studies show that the specific surface area of H3PW12O40 is significantly improved from 5 to 82 (K2.5H0.5PW12O40), 103 (Rb2.5H0.5PW12O40), and 94 m2/g (Cs2.5H0.5PW12O40). XRD, Raman, and FT-IR studies confirm the Keggin structure of all the alkaline metal substituted HPW catalysts. The acidity strengths estimated by NH3-TPD analysis were obtained in the following order: H3PW (2654.91 μmole/g) > K2.5H0.5PW (1060.10 μmole/g) > Rb2.5H0.5PW (762.08 μmole/g) > Cs2.5H0.5.5PW (461.81 μmole/g). Although alkaline metal substituted H3PW12O40 catalysts exhibit higher specific surface area and smaller crystallite size compared to parent H3PW12O40 low glycerol conversions were found for substituted H3PW12O40 catalysts. As well, the parent H3PW12O40 catalyst shows an excellent acrolein selectivity (95%) which is much higher than that of Cs2.5H0.5.5PW (81.9%) and very close to the selectivities obtained over Rb2.5H0.5PW (95.1%) and K2.5H0.5.5PW (95.6%) catalysts. The catalytic performance of H3PW12O40 and M2.5H0.5PW12O40 materials is directly proportional to their acidic strengths, indicating that the catalyst acidity is a key factor for achieving better results in glycerol dehydration. Graphical Abstract Catalytic conversion of glycerol into value-added chemicals, particularly acrolein via acid-catalyzed dehydration route has received much attention due to the potential uses of acrolein. This work reports the synthesis of various alkaline metal substituted phosphotungstic acid (H3PW12O40, HPW) catalysts, namely M2.5H0.5PW12O40 (M = Cs, Rb and K) using a controlled precipitation method. A systematic structural, morphology, and chemical characterization were conducted using various analytical techniques. XRD studies revealed that the incorporation of alkaline metals in H3PW12O40 leads to decreased crystallite size and enhanced lattice strain. N2 adsorption–desorption studies show that the specific surface area of H3PW12O40 is significantly improved from 5 to 82 (K2.5H0.5PW12O40), 103 (Rb2.5H0.5PW12O40), and 94 m2/g (Cs2.5H0.5PW12O40). XRD, Raman, and FT-IR studies confirm the Keggin structure of all the alkaline metal substituted HPW catalysts. The acidity strengths estimated by NH3-TPD analysis were obtained in the following order: H3PW (2654.91 μmole/g) > K2.5H0.5PW (1060.10 μmole/g) > Rb2.5H0.5PW (762.08 μmole/g) > Cs2.5H0.5.5PW (461.81 μmole/g). Although alkaline metal substituted H3PW12O40 catalysts exhibit higher specific surface area and smaller crystallite size compared to parent H3PW12O40 low glycerol conversions were found for substituted H3PW12O40 catalysts. As well, the parent H3PW12O40 catalyst shows an excellent acrolein selectivity (95%) which is much higher than that of Cs2.5H0.5.5PW (81.9%) and very close to the selectivities obtained over Rb2.5H0.5PW (95.1%) and K2.5H0.5.5PW (95.6%) catalysts. The catalytic performance of H3PW12O40 and M2.5H0.5PW12O40 materials is directly proportional to their acidic strengths, indicating that the catalyst acidity is a key factor for achieving better results in glycerol dehydration. Elsevier 2016-12-14 Article PeerReviewed application/pdf en http://eprints.um.edu.my/17419/1/Catalytic_dehydration_of_glycerol_to_acrolein_over_M.pdf Hamid, Sharifah Bee Abd and Daud, N.A. and Suppiah, Durga Devi and Yehya, W.A. and Sudarsanam, P. and Bhargava, S.K. (2016) Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals. Polyhedron, 120. pp. 154-161. ISSN 0277-5387 http://www.sciencedirect.com/science/article/pii/S0277538716303862 https://doi.org/10.1016/j.poly.2016.08.027
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Catalytic dehydration of glycerol to acrolein over M2.5H0.5PW12O40 (M = Cs, Rb and K) phosphotungstic acids: Effect of substituted alkali metals

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