Activation of Cellulose with Alkaline Earth Metals

Alkaline-earth-metal ions accelerate the breaking of cellulose bonds and control the distribution of products in the pyrolysis of lignocellulose to biofuels and chemicals. Here, the activation of cellulose via magnesium ions was measured over a range of temperatures from 370 to 430 degrees C for 20-2000 ms and compared with the activation of cellulose via calcium, another naturally occurring alkaline earth metal in lignocellulose materials. The experimental approach of pulse-heated analysis of solid/surface reactions (PHASRs) showed that magnesium significantly catalyzes cellulose activation with a second-order rate dependence on the catalyst concentration. An experimental barrier of 45.6 +/- 2.1 kcal mol(-1) and a prefactor of 1.18 x 10(16) (mmol Mg2+/g CD)(-2) x s(-1) were obtained for the activation of alpha-cyclodextrin (CD), a cellulose surrogate, for catalyst concentrations of 0.1-0.5 mmol Mg2+ per gram of CD. First-principles density functional theory calculations showed that magnesium ions play a dual role in catalyzing the reaction by breaking the hydrogen bonds with hydroxymethyl groups and destabilizing the reacting cellulose chain, thus making it more active. The calculated barrier of 47 kcal mol(-1) is in agreement with the experimentally measured barriers and similar to that for calcium ion catalysts (similar to 50 kcal mol(-1)).