Recent developments in computational catalysis have allowed the routine reduction of the dimensionality of complex reaction networks to a few descriptors based on linear scaling relations. Despite this convenient benefit, linear scaling relations fundamentally limit the activity and selectivity of a given class of materials towards a given reaction. Here, we show an example by offering a novel description of the fundamental limits on the activity of CO hydrogenation to methanol; a reaction that offers a sustainable route to obtaining value-added chemicals from syngas. First, we show that there is a strong linear correlation between the formation energy of CO* (where * denotes an adsorbed species) and those of the transition states of a number of elementary steps along the methanol synthesis pathway on these surfaces. Using microkinetic modeling, we cast this information into activity volcano plots with the formation energies of a given transition state and CO* as independent descriptors. This analysis reveals the fundamental limits on activity imposed by the aforementioned linear scaling relations, and invites a vigorous search for novel materials that escape these linear scaling relations as a necessary condition for achieving improved activity towards methanol from CO hydrogenation. Specifically, we point out the transition states H–CO* and CH₃O–H* as key transition states to be stabilized independently of CO* for improved activity and selectivity towards methanol synthesis.

计算催化的最新进展已允许将复杂反应网络的维数常规减少到基于线性比例关系的几个描述符。尽管有这种方便的好处，线性比例关系从根本上限制了给定类别的材料对给定反应的活性和选择性。在这里，我们通过提供新颖的描述来举例说明，该描述描述了CO加氢制甲醇活性的基本极限。这种反应为从合成气中获得增值化学品提供了可持续的途径。首先，我们表明，CO *的形成能（其中*表示吸附的物质）与这些表面上沿着甲醇合成途径的许多基本步骤的过渡态的形成能之间存在很强的线性相关性。使用微动力学建模，我们将此信息转换为具有给定过渡态的形成能和CO *作为独立描述符的活动火山图。该分析揭示了由上述线性比例关系施加的活性的基本限制，并引起了对寻找摆脱这些线性比例关系的新颖材料的积极探索，这是获得提高的CO加氢对甲醇活性的必要条件。具体来说，我们指出了过渡态H–CO *和CH 并积极寻求摆脱这些线性比例关系的新型材料，这是实现CO加氢对甲醇活性提高的必要条件。具体来说，我们指出了过渡态H–CO *和CH 并积极寻求摆脱这些线性比例关系的新型材料，这是实现CO加氢对甲醇活性提高的必要条件。具体来说，我们指出了过渡态H–CO *和CH₃ OH *作为关键的过渡态，独立于CO *稳定，以提高活性和对甲醇合成的选择性。