Switching from fossil-based to biomass-based resources implies the development of a new chemistry, involving complex catalytic routes. The transformation of polyols, as sugars, into carbohydrates is of course already feasible. New heterogeneous catalysts will lead to more efficient processes, and therefore to more sustainable energy resources. Oil-based chemistry is usually done in organic solvents, whereas biomass products are almost always solvated in water. The presence of water can dramatically change the behaviour of metallic supported catalysts.[C. Michel et al. Chem. Commun., 2014,50] Understanding the solvent effects and exploring the reactions routes are the major challenges, and also the more complex, for designing efficient new catalysts. The case of the oxidative dehydrogenation of butanediols is a good starting point, as it is a relatively simple system, but complex enough to study chemoselectivity towards the two alcohol groups, depending on their relative positions. Aiming at developing a rational simulation method, the first step was to define the best compromise in cost and efficiency to model the solvation energy. We compared two approaches: (i) a continuum approach as implemented recently in the periodic DFT program VASP [Kiran Mathew et al. J. Chem. Phys. 140, 084106 2014] (ii) a discrete approach based on alchemical transformation inspired by the work of Muhammad Faheem and Andreas Heyden [J. Chem. Theory Comput., 2014, 10 (8)] to better include the possible H-bond between the alcohol function and water molecules. The adsorption energies of the budanediol and the reaction intermediate and products are more or less impacted by the solvation energy, possibly modifying the reaction path and the predicted activity and selectivity. This takes us a step closer in the quest for highly efficient and environment friendly catalysts.

Simulations of reactivity at complex interfaces: Catalytic conversion of biomass derived alcohols at Pt/H2O interface

251st National Meeting (2016)

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