Rational design of selective metal catalysts for alcohol amination with ammonia

International audienceThe lack of selectivity for the direct amination of alcohols with ammonia, a modern and clean route for the synthesis of primary amines, is an unsolved challenge. Here, we combine first-principles calculations, scaling relations, kinetic simulations and catalysis experiments to unveil the key factors governing the activity and selectivity of metal catalysts for this reaction. We show that the loss of selectivity towards primary amines is linked to a surface-mediated C-N bond coupling between two N-containing intermediates: CH 3 NH and CH 2 NH. The barrier for this step is low enough to compete with the main surface hydrogenation reactions and can be used as a descriptor for selectivity. The combination of activity and selectivity maps using the C and O adsorption energies as descriptors is used for the computational screening of 348 dilute bimetallic catalysts. Among the best theoretical candidates, Co 98.5 Ag 1.5 and Co 98.5 Ru 1.5 (5 wt% Co) are identified as the most promising catalysts from experiments