Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid

Fenfen Wang; Zhijie Chen; Haoyuan Chen; Timothy A. Goetjen; Peng Li; Xingjie Wang; Selim Alayoglu; Kaikai Ma; Yongwei Chen; Tiejun Wang; Timur Islamoglu; Yanxiong Fang; Randall Q. Snurr; Omar K. Farha

doi:10.1021/acsami.9b07769

Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid

Fenfen Wang, Zhijie Chen, Haoyuan Chen, Timothy A. Goetjen, Peng Li, Xingjie Wang, Selim Alayoglu, Kaikai Ma, Yongwei Chen, Tiejun Wang, Timur Islamoglu, Yanxiong Fang, Randall Q. Snurr, Omar K. Farha^*

^*Corresponding author for this work

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

8 Scopus citations

Abstract

We report the performance of UiO-66 and its Brønsted acid functionalized derivative, UiO-66-(COOH)₂, as heterogeneous catalysts for levulinic acid esterification with ethanol. Importantly, compared with UiO-66, UiO-66-(COOH)₂ displayed superior catalytic performance (up to 97.0 ± 1.1% yield of ethyl levulinate) attributed to the synergistic effect between Lewis acidic Zr clusters and Brønsted acidic -COOH groups. Furthermore, UiO-66-(COOH)₂ was stable and reusable without an appreciable loss in catalytic activity for at least five consecutive cycles. This study demonstrates that the interplay of Brønsted and Lewis acid sites in zirconium metal-organic frameworks leads to more efficient catalytic conversion of a biomass feedstock to biofuel, and with further hypothesis driven research, additional materials that show promise as candidates for catalytic conversion of biomass feedstocks to biofuels and valuable chemicals can be developed.

Original language	English (US)
Pages (from-to)	32090-32096
Number of pages	7
Journal	ACS Applied Materials and Interfaces
Volume	11
Issue number	35
DOIs	https://doi.org/10.1021/acsami.9b07769
State	Published - Sep 4 2019

Keywords

esterification
ethyl levulinate
heterogeneous catalysis
levulinic acid
metal-organic framework

ASJC Scopus subject areas

Materials Science(all)

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10.1021/acsami.9b07769

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Wang, F., Chen, Z., Chen, H., Goetjen, T. A., Li, P., Wang, X., Alayoglu, S., Ma, K., Chen, Y., Wang, T., Islamoglu, T., Fang, Y., Snurr, R. Q., & Farha, O. K. (2019). Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid. ACS Applied Materials and Interfaces, 11(35), 32090-32096. https://doi.org/10.1021/acsami.9b07769

Wang, Fenfen ; Chen, Zhijie ; Chen, Haoyuan ; Goetjen, Timothy A. ; Li, Peng ; Wang, Xingjie ; Alayoglu, Selim ; Ma, Kaikai ; Chen, Yongwei ; Wang, Tiejun ; Islamoglu, Timur ; Fang, Yanxiong ; Snurr, Randall Q. ; Farha, Omar K. / Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid. In: ACS Applied Materials and Interfaces. 2019 ; Vol. 11, No. 35. pp. 32090-32096.

@article{2db697a2b0a94dcfb4fe9f4551049c39,

title = "Interplay of Lewis and Br{\o}nsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid",

abstract = "We report the performance of UiO-66 and its Br{\o}nsted acid functionalized derivative, UiO-66-(COOH)2, as heterogeneous catalysts for levulinic acid esterification with ethanol. Importantly, compared with UiO-66, UiO-66-(COOH)2 displayed superior catalytic performance (up to 97.0 ± 1.1% yield of ethyl levulinate) attributed to the synergistic effect between Lewis acidic Zr clusters and Br{\o}nsted acidic -COOH groups. Furthermore, UiO-66-(COOH)2 was stable and reusable without an appreciable loss in catalytic activity for at least five consecutive cycles. This study demonstrates that the interplay of Br{\o}nsted and Lewis acid sites in zirconium metal-organic frameworks leads to more efficient catalytic conversion of a biomass feedstock to biofuel, and with further hypothesis driven research, additional materials that show promise as candidates for catalytic conversion of biomass feedstocks to biofuels and valuable chemicals can be developed.",

keywords = "esterification, ethyl levulinate, heterogeneous catalysis, levulinic acid, metal-organic framework",

author = "Fenfen Wang and Zhijie Chen and Haoyuan Chen and Goetjen, {Timothy A.} and Peng Li and Xingjie Wang and Selim Alayoglu and Kaikai Ma and Yongwei Chen and Tiejun Wang and Timur Islamoglu and Yanxiong Fang and Snurr, {Randall Q.} and Farha, {Omar K.}",

year = "2019",

month = sep,

day = "4",

doi = "10.1021/acsami.9b07769",

language = "English (US)",

volume = "11",

pages = "32090--32096",

journal = "ACS applied materials & interfaces",

issn = "1944-8244",

publisher = "American Chemical Society",

number = "35",

}

Wang, F, Chen, Z, Chen, H, Goetjen, TA, Li, P, Wang, X, Alayoglu, S, Ma, K, Chen, Y, Wang, T, Islamoglu, T, Fang, Y, Snurr, RQ & Farha, OK 2019, 'Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid', ACS Applied Materials and Interfaces, vol. 11, no. 35, pp. 32090-32096. https://doi.org/10.1021/acsami.9b07769

Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid. / Wang, Fenfen; Chen, Zhijie; Chen, Haoyuan; Goetjen, Timothy A.; Li, Peng; Wang, Xingjie; Alayoglu, Selim; Ma, Kaikai; Chen, Yongwei; Wang, Tiejun; Islamoglu, Timur; Fang, Yanxiong; Snurr, Randall Q.; Farha, Omar K.

In: ACS Applied Materials and Interfaces, Vol. 11, No. 35, 04.09.2019, p. 32090-32096.

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

TY - JOUR

T1 - Interplay of Lewis and Brønsted Acid Sites in Zr-Based Metal-Organic Frameworks for Efficient Esterification of Biomass-Derived Levulinic Acid

AU - Wang, Fenfen

AU - Chen, Zhijie

AU - Chen, Haoyuan

AU - Goetjen, Timothy A.

AU - Li, Peng

AU - Wang, Xingjie

AU - Alayoglu, Selim

AU - Ma, Kaikai

AU - Chen, Yongwei

AU - Wang, Tiejun

AU - Islamoglu, Timur

AU - Fang, Yanxiong

AU - Snurr, Randall Q.

AU - Farha, Omar K.

PY - 2019/9/4

Y1 - 2019/9/4

N2 - We report the performance of UiO-66 and its Brønsted acid functionalized derivative, UiO-66-(COOH)2, as heterogeneous catalysts for levulinic acid esterification with ethanol. Importantly, compared with UiO-66, UiO-66-(COOH)2 displayed superior catalytic performance (up to 97.0 ± 1.1% yield of ethyl levulinate) attributed to the synergistic effect between Lewis acidic Zr clusters and Brønsted acidic -COOH groups. Furthermore, UiO-66-(COOH)2 was stable and reusable without an appreciable loss in catalytic activity for at least five consecutive cycles. This study demonstrates that the interplay of Brønsted and Lewis acid sites in zirconium metal-organic frameworks leads to more efficient catalytic conversion of a biomass feedstock to biofuel, and with further hypothesis driven research, additional materials that show promise as candidates for catalytic conversion of biomass feedstocks to biofuels and valuable chemicals can be developed.

AB - We report the performance of UiO-66 and its Brønsted acid functionalized derivative, UiO-66-(COOH)2, as heterogeneous catalysts for levulinic acid esterification with ethanol. Importantly, compared with UiO-66, UiO-66-(COOH)2 displayed superior catalytic performance (up to 97.0 ± 1.1% yield of ethyl levulinate) attributed to the synergistic effect between Lewis acidic Zr clusters and Brønsted acidic -COOH groups. Furthermore, UiO-66-(COOH)2 was stable and reusable without an appreciable loss in catalytic activity for at least five consecutive cycles. This study demonstrates that the interplay of Brønsted and Lewis acid sites in zirconium metal-organic frameworks leads to more efficient catalytic conversion of a biomass feedstock to biofuel, and with further hypothesis driven research, additional materials that show promise as candidates for catalytic conversion of biomass feedstocks to biofuels and valuable chemicals can be developed.

KW - esterification

KW - ethyl levulinate

KW - heterogeneous catalysis

KW - levulinic acid

KW - metal-organic framework

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U2 - 10.1021/acsami.9b07769

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