Although non-noble metal catalysts are appealing for propane dehydrogenation, achieving high propylene selectivity remains a persistent challenge, which necessitates the regulation of catalytic microenvironment. In this study, we comparatively investigate three commonly used active metals (Pt, Pd, and non-noble metal Ni) using both theoretical and experimental approaches. We find that the low selectivity of Ni-based catalysts is intrinsically attributed to a narrow interatomic distance (Δd) between Ni atoms, which promotes side reactions. Thus, Ni-based intermetallic alloys are employed to modulate Δd, whose surface microenvironment is quantified with a descriptor called degree-of-isolation. The established volcano-shaped isolation-selectivity plot provides a direct avenue for predicting propylene selectivity, which is determined by two competing variables: desorption and further dehydrogenation of propylene. The optimal catalyst, NiIn, manifests moderate Ni–C repulsion, obtaining >91% experimental propylene selectivity. This reveals the Sabatier principle over Ni-based catalysts for selective propane dehydrogenation and underscores the significance of microenvironment engineering.

尽管非贵金属催化剂对丙烷脱氢很有吸引力，但实现高丙烯选择性仍然是一个持续的挑战，这需要催化微环境的调控。在本研究中，我们利用理论和实验方法对三种常用的活性金属（Pt、Pd 和非贵金属 Ni）进行了比较研究。我们发现镍基催化剂的低选择性本质上是由于镍原子之间的原子间距离（ Δd ）较窄，从而促进了副反应。因此，采用镍基金属间合金来调节 Δ d ，其表面微环境通过称为隔离度的描述符进行量化。所建立的火山形分离选择性图为预测丙烯选择性提供了直接途径，丙烯选择性由两个相互竞争的变量决定：丙烯的解吸和进一步脱氢。最佳催化剂 NiIn 表现出中等的 Ni-C 排斥力，获得 >91% 的实验丙烯选择性。这揭示了用于选择性丙烷脱氢的镍基催化剂的萨巴蒂尔原理，并强调了微环境工程的重要性。