Energy transition is a challenge that we are facing today and one aspect is the production of valuable chemicals from other resources than oil. This can be achieved by the conversion of lignocellulosic biomass. However, these processes are not yet established. Hence, identifying efficient catalytic routes would lead to major improvements and benefits to society. The typical process implies hydrodeoxygenation (HDO) of lignocellulose sub products. The description at the Density Functional Theory (DFT) is extremely costly in terms of computational effort, the number of possible structures and routes being numerous. Furthermore, lignocellulosic biomass conversion involves aqueous media, known to drastically change the behaviour of known catalysts. Therefore, a fast estimating method, like group additivity, would be helpful to screen large reaction networks, identifying the most promising routes which then can be investigated in more detail by more accurate DFT computations, including explicit solvation effects. The model we build relies on 164 DFT results, including gas phase species, ethanol decomposition fragments, and randomly selected erythritol derivates. Adsorption energies on Pt(111), are taking into account for dispersion interactions and solvation effects. As a first step to large scale screening, the GA model predicts the solvation and dispersion energy contributions or total heat of formations, of gas phase and adsorbed species on a Pt(111) surface. With a mean absolute deviation of 3.75 kcal/mol on the heat of formation for the training set for instance, our model provides a reliable starting point for screening possible reactions. The validation has been done on various isomers and their conformations of butandiols, and their dehydrogenated products. Furthermore, our work highlights the importance of accounting for solvation, in particular for reactions involving O-H bond breakings. The formation of internal H bonds is driven by the spacing between the -OH groups and the solvation, depending on whether H bonding or solvent exposure is the most favorable interaction.

Group additivity for adsorbed polyols at a Pt(111) surface under aqueous conditions

253rd National Meeting (2017)

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