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Synthesis of Hierarchical Sn-MFI as Lewis Acid Catalysts for Isomerization of Cellulosic Sugars

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journal contribution
posted on 06.06.2014, 00:00 by Hong Je Cho, Paul Dornath, Wei Fan
Hierarchical stannosilicate molecular sieves with ordered mesoporosity and MFI topology (three dimensionally ordered mesoporous imprinted (3DOm-i) Sn-MFI) were successfully synthesized within the confined space of three dimensionally ordered mesoporous (3DOm) carbon by a seeded growth method. The obtained 3DOm-i Sn-MFI consisting of 30 nm spherical elements forming an opaline structure contains highly ordered mesopores ranging from 4 to 11 nm. Compared with conventional Sn-MFI, 3DOm-i Sn-MFI exhibits superior catalytic performance for the isomerization of cellulosic sugars. No diffusion limitation was observed for the isomerization of a triose sugar, dihydroxyacetone (DHA), into methyl lactate (ML). The presence of weak Brønsted acid in the 3DOm-i Sn-MFI catalyst facilitates the reaction by catalyzing the formation of an intermediate, pyruvaldehyde (PA). 3DOm-i Sn-MFI offers significant improvements for the isomerizations of C5 and C6 sugars, such as xylose and glucose, by greatly enhancing molecular transport. The reaction rate of xylose on 3DOm-i Sn-MFI is at least 20 times higher than that on conventional bulky sized Sn-MFI. The reaction rate for glucose is also enhanced by using 3DOm-i Sn-MFI, but to a lesser extent as compared with the reaction of xylose, possibly because glucose cannot diffuse into the 10-membered-ring pore of MFI, and the reaction is catalyzed only on the external surface of the Sn-MFI catalysts. Moreover, the combination of seeded growth with confined synthesis allows us to synthesize hierarchical Sn-MFI using commercially available carbon materials, such as carbon black and activated carbon, indicating that the synthesis strategy is a versatile and reliable method for tailoring the structure of hierarchical zeolites.