Tin-containing zeolite for the isomerization of cellulosic sugars

Lew, Christopher M.; Rajabbeigi, Nafiseh; Tsapatsis, Michael

doi:10.1016/j.micromeso.2011.12.020

Cited by 119 publications

(114 citation statements)

References 36 publications

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“…9 Other zeolites modified with Sn have also been considered for sugar conversions. [10][11][12][13][14] Sn (and Ti)-modified MFI zeolites, which have narrower pores than Beta zeolite, were found to be inactive for glucose isomerization. 9,12 Although the glucose isomerization activity of Sn-modified MWW zeolite was very low, 11 this catalyst was highly active for the retro-aldolization of sugars to methyl lactate in methanol.…”

Section: Introductionmentioning

confidence: 99%

Influence of pore topology on synthesis and reactivity of Sn-modified zeolite catalysts for carbohydrate conversions

Graaff

Tempelman

Pidko

et al. 2017

Catal. Sci. Technol.

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A range of Sn-modified MWW, MFI, MOR and Beta zeolites were prepared by a post-synthetic Sn functionalization method and their catalytic properties for sugar conversions were evaluated. The focus of this work was to understand the effect of micropore dimensions and additional mesoporosity on the Sn incorporation and on the catalytic properties. The post-synthetic approach, which involves aciddealumination of the parent zeolite followed by SnCl 4 grafting, is highly efficient for the selective incorporation of lattice Sn sites in wide-pore Beta and MOR zeolites. The modification of the medium-pore MWW and MFI is impaired by the more difficult dealumination and hence the lower efficiency of the Sn incorporation. Hierarchical structuring of the zeolites allows the increase of the Sn loading in the final zeolites. The catalytic properties were assessed in the isomerization and retro-aldolization reactions of glucose and the conversion of 1,3-dihydroxyacetone to methyl lactate. The catalytic results depend strongly on the structural and topological properties of the catalysts as well as on the reactant. Glucose isomerization carried out at a relatively low temperature is mainly limited by strong adsorption of carbohydrates to the active sites. This explains why zeolite nanostructuring had little effect on the catalyst activity, which instead depends mainly on the zeolite topology and the nature of the reactive Sn centers. The influence of pore size is most pronounced for Sn-MWW and Sn-MFI zeolites which are inactive in glucose-to-fructose isomerization, but perform in the higher-temperature retro-aldolization of carbohydrates with an activity similar to that of Sn-Beta. Because of the limited accessibility of the Sn sites inside the 1D MOR pore system, Sn-MOR catalysts were only moderately active in all probe reactions considered.

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Section: Introductionmentioning

confidence: 99%

Influence of pore topology on synthesis and reactivity of Sn-modified zeolite catalysts for carbohydrate conversions

Graaff

Tempelman

Pidko

et al. 2017

Catal. Sci. Technol.

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“…It has been shown that the isomerization activities of other Sn-modified silicates such as Sn-MCM-41 and Sn-MFI are much lower. [19,22] Although substantial progress has been made in understanding the catalytic chemistry of sugars by Sn-BEA, there are several important issues that have yet to be resolved. First of all, the nature of the active site for glucose isomerization has not been unambiguously determined.…”

Section: Introductionmentioning

confidence: 99%

The Mechanism of Glucose Isomerization to Fructose over Sn‐BEA Zeolite: A Periodic Density Functional Theory Study

Yang¹,

Pidko²,

Hensen³

2013

ChemSusChem

131

165

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The isomerization of glucose to fructose in the presence of Sn-containing zeolite BEA (beta polymorph A) was studied by periodic DFT calculations. Focus was placed on the nature of the active site and the reaction mechanism. The reactivities of the perfect lattice Sn(IV) site and the hydroxylated SnOH species are predicted to be similar. The isomerization activity of the latter can be enhanced by creating an extended silanol nest in its vicinity. Besides the increased Lewis acidity and coordination flexibility of the Sn center, the enhanced reactivity in this case is ascribed to the reaction environment that promotes activation of the confined sugar intermediates through hydrogen bonding. The resulting multidentate activation of the substrate favors the rate-determining hydrogen-shift reaction. These findings suggest the important role of defect lattice sites in Sn-BEA for catalytic glucose isomerization.

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“…[29][30][31][32][33][34] Another issue with BEA zeolite is that the incorporation of heteroatoms in its lattice requires long synthesis times and especially the incorporation of significant amounts of Lewis acid sites is challenging. [35,36] An additional drawback concerning the preparation of Sn-modified BEA zeolite is the use of HF, which is undesired because of environmental reasons. [36,37] The exploration of a bifunctional Sn-MCM-41 silica catalyst by Sels et al avoids the use of BEA zeolite; however, in this case the challenge is to carefully control the mild Brønsted acidity.…”

mentioning

confidence: 99%

“…[35,36] An additional drawback concerning the preparation of Sn-modified BEA zeolite is the use of HF, which is undesired because of environmental reasons. [36,37] The exploration of a bifunctional Sn-MCM-41 silica catalyst by Sels et al avoids the use of BEA zeolite; however, in this case the challenge is to carefully control the mild Brønsted acidity. [24] Herein, we report on our efforts to synthesize a Sn-containing MWW zeolite with a low concentration of defect sites in which the heteroatom incorporation is performed by using a straightforward postsynthetic modification method.…”

mentioning

confidence: 99%

Highly Active and Recyclable Sn‐MWW Zeolite Catalyst for Sugar Conversion to Methyl Lactate and Lactic Acid

et al. 2013

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Not just sugar! Lewis‐acidic Sn‐MWW zeolites are obtained through postsynthesis functionalization of deboronated B‐MWW with Sn. These materials are highly active, selective, and recyclable catalysts for the conversion of triose sugars to methyl lactate (in methanol) and lactic acid (in water). They also demonstrate good performance in the conversion of hexose sugars and sucrose to methyl lactate.

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Tin-containing zeolite for the isomerization of cellulosic sugars

Cited by 119 publications

References 36 publications

Influence of pore topology on synthesis and reactivity of Sn-modified zeolite catalysts for carbohydrate conversions

Influence of pore topology on synthesis and reactivity of Sn-modified zeolite catalysts for carbohydrate conversions

The Mechanism of Glucose Isomerization to Fructose over Sn‐BEA Zeolite: A Periodic Density Functional Theory Study

Highly Active and Recyclable Sn‐MWW Zeolite Catalyst for Sugar Conversion to Methyl Lactate and Lactic Acid

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