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Ab initio methods were used to study the coordination of electron donors to the (110) and (101) surfaces of a MgCl2 support. The electron donors were alcohols, ketones, esters, and their model compounds. Examination of the interaction energies indicated that the alcohols bind more strongly to the five-coordinated magnesium atom on the (101) surface than to the four-coordinated magnesium atom on the (110) surface. This stability on the (101) surface can be explained in terms of hydrogen bonding between the complexed alcohol and a chloride ion of the surface. Like the alcohols, the esters form the most stable complexes on the (101) surface. In contrast, the ketones coordinate preferably to the (110) surface. The geometries of these coordinated electron donors can be predicted fairly reliably even with small model compounds. In the case of the alcohols, the coordination angle between the donor and the surface depends on the number of alcohols on the same magnesium atom.

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Green chemistry, sustainability and eco-efficiency are guiding the development of the next generation of industrial chemical processes. The use of non-edible lignocellulosic biomass as a source of chemicals and fuels has recently raised interest due to the need for an alternative to fossil resources. Valorisation mainly focuses on cellulose, which has been used for various industrial scale applications for decades. However, creating an economically more viable value chain would require the exploitation of the other main components, hemicellulose and lignin. Here, we present a new low melting mixture composition based in boric acid and choline chloride, and demonstrate its efficiency in the fractionation of wood-based biomass for the production of non-condensed lignin, suitable for further use in the search for sustainable industrial applications, and for the selective conversion of hemicelluloses into valuable platform chemicals.

The swelling and cation exchange properties of montmorillonite are fundamental in a wide range of applications ranging from nanocomposites to catalytic cracking of hydrocarbons. The swelling results from several factors and, though widely studied, information on the effects of a single factor at a time is lacking. In this study, density functional theory (DFT) calculations were used to obtain atomic-level information on the swelling of montmorillonite. Molecular dynamics (MD) was used to investigate the swelling properties of montmorillonites with different layer charges and interlayer cationic compositions. Molecular dynamics calculations, with CLAYFF force field, consider three layer charges (−1.0, −0.66 and −0.5 e per unit cell) arising from octahedral substitutions and interlayer counterions of Na, K and Ca. The swelling curves obtained showed that smaller layer charge results in greater swelling but the type of the interlayer cation also has an effect. The DFT calculations were also seen to predict larger d values than MD. The formation of 1, 2 and 3 water molecular layers in the interlayer spaces was observed. Finally, the data from MD calculations were used to predict the selfdiffusion coefficients of interlayer water and cations in different montmorillonites and in general the coefficient increased with increasing water content and with decreasing layer charge.