Heterolytic C-H Activation Routes in Catalytic Dehydrogenation of Light Alkanes on Lewis Acid-Base Pairs at ZrO₂...

Alkane dehydrogenation is an enabling route to make alkenes useful as chemical intermediates. This study demonstrates the high reactivity of Lewis acid-base (LAB) site pairs at ZrO₂ powders for dehydrogenation of C₂-C₄ alkanes and the essential requirement for chemical treatments to remove strongly bound H₂O and CO₂ titrants to avoid the high temperatures required for their desorption and the concomitant loss of active sites through sintering and annealing of ZrO₂ crystallites. The energies and free energies of bound intermediates and transition states from density functional theory (DFT), taken together with kinetic analysis and isotopic methods, demonstrated the kinetic relevance and heterolytic character of the first C-H activation at terminal C-atoms for all alkanes with a modest activation barrier (84 kJ mol^-1) at essentially bare Zr-O LAB site pairs. β-Hydride elimination from the formed alkyl carbanions lead to their desorption as alkene products in steps that are favored over their parallel C-C cleavage reactions (by 100 kJ mol^-1), leading to high dehydrogenation selectivities (>98%) at the temperatures required for practical yields in such endothermic dehydrogenation reactions (700-900 K). The facile recombination of bound proton-hydride pairs then completes a dehydrogenation turnover. These findings provide compelling evidence for the remarkable reactivity and selectivity of LAB sites on earth-abundant oxides and for the need to uncover them through chemical treatments, which combine to give gravimetric dehydrogenation rates that exceed those on the toxic (Cr) or costly (Pt) catalysts used in practice.