Controlling the precise atomic architecture of supported metals is central to optimizing their catalytic performance, as recently exemplified for nanostructured platinum and ruthenium systems in acetylene hydrochlorination, a key process for vinyl chloride production. This opens the possibility of building on historically established activity correlations. In this study, we derived quantitative activity, selectivity and stability descriptors that account for the metal-dependent speciation and host effects observed in acetylene hydrochlorination. To achieve this, we generated a platform of Au, Pt, Ru, Ir, Rh and Pd single atoms and nanoparticles supported on different types of carbon and assessed their evolution during synthesis and under the relevant reaction conditions. Combining kinetic, transient and chemisorption analyses with modelling, we identified the acetylene adsorption energy as a speciation-sensitive activity descriptor, further determining catalyst selectivity with respect to coke formation. The stability of the different nanostructures is governed by the interplay between single atom–support interactions and chlorine affinity, promoting metal redispersion or agglomeration, respectively.

控制负载金属的精确原子结构对于优化其催化性能至关重要，最近在乙炔氢氯化中的纳米结构铂和钌系统就是一个例子，这是氯乙烯生产的关键过程。这开启了建立在历史上建立的活动相关性的可能性。在这项研究中，我们得出了定量活性、选择性和稳定性描述符，这些描述符解释了在乙炔氢氯化中观察到的金属依赖性物种形成和宿主效应。为了实现这一目标，我们生成了一个由 Au、Pt、Ru、Ir、Rh 和 Pd 单原子和纳米颗粒支撑在不同类型碳上的平台，并评估了它们在合成过程中和相关反应条件下的演化。将动力学、瞬态和化学吸附分析与建模相结合，我们将乙炔吸附能确定为对物种形成敏感的活性描述符，进一步确定了催化剂对焦炭形成的选择性。不同纳米结构的稳定性受单原子-载体相互作用和氯亲和力之间的相互作用控制，分别促进金属再分散或团聚。