Decoupling the electronic and geometric effects has been a long cherished goal for heterogeneous catalysis due to their tangled relationship. Here, a novel orthogonal decomposition method is firstly proposed to settle this issue in p-chloronitrobenzene hydrogenation reaction on size- and shape-controlled Pt nanoparticles (NPs) carried on various supports. Results suggest Fermi levels of catalysts can be modulated by supports with varied work function (W_f). And the selectivity on Pt NPs of similar size and shape is linearly related with the W_f of support. Optimized Fermi levels of the catalysts with large W_f weaken the ability of Pt NPs to fill valence electrons into the antibonding orbital of C–Cl bond, finally suppressing the hydrodehalogenation side reaction. Foremost, the geometric effect is firstly spun off through orthogonal relation based on series of linear relationships over various sizes of Pt NPs reflecting the electronic effect. Moreover, separable nested double coordinate system is established to quantitatively evaluate the two effects.

由于它们之间错综复杂的关系，将电子和几何效应解耦一直是多相催化的长期目标。在这里，首先提出了一种新的正交分解方法，以解决在各种载体上承载尺寸和形状可控的 Pt 纳米粒子 (NPs) 上的对氯硝基苯加氢反应中的这一问题。结果表明催化剂的费米能级可以通过具有不同功函数 ( W _f ) 的载体来调节。并且对类似尺寸和形状的 Pt NPs 的选择性与载体的W _f线性相关。具有大W _{f的催化剂的优化费米能级}削弱了 Pt NPs 将价电子填充到 C-Cl 键的反键轨道中的能力，最终抑制了加氢脱卤副反应。首先，几何效应首先是通过基于反映电子效应的各种尺寸 Pt NPs 上的一系列线性关系的正交关系分离出来的。此外，建立了可分离的嵌套双坐标系来定量评估这两种效果。