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Challenges of and Insights into Acid-Catalyzed Transformations of Sugars

Caratzoulas, Stavros and Davis, Mark E. and Gorte, Raymond J. and Gounder, Rajamani and Lobo, Raul F. and Nikolakis, Vladimiros and Sandler, Stanley I. and Snyder, Mark A. and Tsapatsis, Michael and Vlachos, Dionisios G. (2014) Challenges of and Insights into Acid-Catalyzed Transformations of Sugars. Journal of Physical Chemistry C, 118 (40). pp. 22815-22833. ISSN 1932-7447. https://resolver.caltech.edu/CaltechAUTHORS:20141113-125440628

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Abstract

The selective transformation of hexose and pentose sugars to intermediate platform chemicals, such as furans, is an essential step in the conversion of cellulosic and hemicellulosic biomass to biofuels and biochemicals. Yet, many challenges in achieving commercially viable processes remain. In this feature article, we outline challenges that need to be overcome to enable these transformations. Then, we present the newly introduced acid-catalyzed isomerization of aldose sugars to ketose sugars via a class of solid Lewis acid catalysts (e.g., Sn-Beta, Ti-Beta). We elucidate mechanistic insights arising from subnanometer cooperativity and solvent effects that can be controlled to tune reaction pathways and selectivity and draw parallels between heterogeneous and homogeneous Lewis acid catalysts. Subsequently, we discuss fructose dehydration to 5-hydroxyl-methylfurfural (HMF) via homogeneous and heterogeneous Brønsted acid-catalyzed chemistry. We show how fundamental insights arising from the combination of kinetics, spectroscopy, and multiscale simulations rationalize the improved yield of HMF in water–organic cosolvents. The stability of heterogeneous Lewis acid catalysts under low pH enables tandem Brønsted and Lewis acid-catalyzed reactions in a single pot that overcomes equilibrium limitations and gives a high HMF yield starting from sugar raw materials. Additionally, we provide an overview of multicomponent adsorption of biomass derivatives from solution in microporous materials and discuss how structure–property relations can lead to superior micro- and micromesoporous carbon adsorbents for reactive adsorption toward high HMF yield. Finally, we provide an outlook for the field.


Item Type:Article
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http://dx.doi.org/10.1021/jp504358d DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp504358dPublisherArticle
Additional Information:© 2014 American Chemical Society. ACS Editors' Choice - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Received: May 4, 2014; Revised: July 21, 2014; Published: July 24, 2014. We acknowledge support from the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0001004.
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Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0001004
Issue or Number:40
Record Number:CaltechAUTHORS:20141113-125440628
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141113-125440628
Official Citation:Challenges of and Insights into Acid-Catalyzed Transformations of Sugars Stavros Caratzoulas, Mark E. Davis, Raymond J. Gorte, Rajamani Gounder, Raul F. Lobo, Vladimiros Nikolakis, Stanley I. Sandler, Mark A. Snyder, Michael Tsapatsis, and Dionisios G. Vlachos The Journal of Physical Chemistry C 2014 118 (40), 22815-22833
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:51712
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:13 Nov 2014 21:19
Last Modified:03 Oct 2019 07:35

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