The 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 problem. Here, we combine first-principles calculations, scaling relations, kinetic simulations and catalysis experiments to determine the key factors that govern 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: CH₃NH and CH₂NH. The barrier for this step is low enough to compete with the main surface hydrogenation reactions and it can be used as a descriptor for selectivity. The activity and selectivity maps (using the C and O adsorption energies as descriptors) were combined for the computational screening of 348 dilute bimetallic catalysts. Among the best theoretical candidates, Co_98.5Ag_1.5 and Co_98.5Ru_1.5 (5 wt% Co) were identified experimentally to be the most promising catalysts.

醇与氨直接胺化的选择性缺乏（用于合成伯胺的现代且清洁的途径）是未解决的问题。在这里，我们结合第一性原理计算，比例关系，动力学模拟和催化实验来确定控制该反应金属催化剂的活性和选择性的关键因素。我们表明，对伯胺的选择性损失与两个含氮中间体CH ₃ NH和CH ₂之间的表面介导的C–N键偶联相关NH。该步骤的势垒低到足以与主表面氢化反应竞争，它可以用作选择性的描述。结合了活性和选择性图（使用C和O的吸附能作为描述符）对348种稀双金属催化剂进行了计算筛选。在最佳理论候选物中，实验确定Co _98.5 Ag _1.5和Co _98.5 Ru _1.5（5 wt％Co）是最有前途的催化剂。