Reaction rates in a two-step catalytic sequence, when plotted vs adsorption energy of the key or the most abundant surface intermediate, result in volcano shaped curves. In the current work, the optimal catalyst is discussed for structure sensitive reactions, which display dependence of activity on the cluster size of the active catalytic phase. An expression is derived relating the Gibbs energy for formation of the intermediate with the Gibbs energy changes in the overall reaction, difference in adsorption thermodynamics on edges and terraces and the cluster size. The kinetic expressions display dependence of activity vs the Gibbs energy of the adsorbed intermediate formation. Numerical analysis demonstrates that when the overall equilibrium constant K is high and the reaction is thermodynamically very favorable, the maxima in the rates vs the adsorption constant for the optimal catalyst are much broader being less dependent on the cluster size. When structure sensitivity is pronounced, there are smaller differences in the rates for the optimum and less optimal catalysts in comparison with reactions showing weak structure sensitivity.

当绘制两步催化序列中的反应速率与关键或最丰富的表面中间体的吸附能的关系图时，会形成火山形曲线。在当前的工作中，讨论了对结构敏感的反应的最佳催化剂，该反应显示了活性对活性催化相簇尺寸的依赖性。得出一个表达式，将形成中间体的吉布斯能量与整个反应中的吉布斯能量变化，边缘和台阶上的吸附热力学差异以及团簇大小相关。动力学表达式显示出活性对吸附的中间形成物的吉布斯能量的依赖性。数值分析表明，当总平衡常数K高且反应在热力学上非常有利时，最佳催化剂的速率与吸附常数的最大值之间的关系要宽得多，对簇尺寸的依赖性较小。当显着的结构敏感性时，与显示弱的结构敏感性的反应相比，最佳和次佳催化剂的速率差异较小。