Production of aromatics from biomass by computer-aided selection of the zeolite catalyst

[EN] Taking into account that the transformation of biomass-derived 2,5-dimethylfuran (DMF) top-xylene involves Diels-Alder (DA) cycloaddition as the limiting step, the use of an ITQ-2 zeolite obtained by direct synthesis (DS-ITQ-2) as a catalyst for this reaction is proposed based on the fact that the organic molecule employed for its synthesis mimics the size and shape of the DA oxanorbornene cycloadduct intermediate. Periodic Density Functional Theory (DFT) calculations reveal a better stabilization of the oxanorbornene intermediate within the external hemicavities or "cups" of the DS-ITQ-2 zeolite (MWW-framework) than in other zeolites employed for this reaction, such as FAU and Beta. Interestingly, experimental results also show improved catalytic conversion values for the DS-ITQ-2 zeolite compared to FAU and Beta, in good agreement with the stabilization energies calculated by DFT. The "ab initio" catalyst design presented here to enhance the catalytic performance for the transformation of biomass-derived products is a valuable example that could be employed for the rationalization of other chemical processes catalyzed by zeolites.This work has been supported by the European Union through ERC-AdG-2014-671093 (SynCatMatch) and by Spanish Government through "Severo Ochoa" (SEV-2016-0683, MINECO), MAT2017-82288-C2-1-P (AEI/FEDER, UE) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE). E. M. G. acknowledges "La Caixa - Severo Ochoa" International PhD Fellowships (call 2015). Elisa Garcia is acknowledged for her technical assistance in this work. The Electron Microscopy Service of the UPV is also acknowledged for their help in sample characterization. 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