Controlling the precise atomic architectures of supported metals is central to unlock their potential as heterogeneous catalysts, as recently exemplified for nanostructured platinum and ruthenium systems in acetylene hydrochlorination, a key industrial technology for vinyl chloride production. This opens the possibility to build on historically established activity correlations. Here, we derive quantitative activity, selectivity, and stability descriptors, accounting for the metal-dependent speciation and host effects. To achieve this, we generate a platform of Au, Pt, Ru, Ir, Rh, and Pd single atoms and nanoparticles supported on functionalized carbons and assess their evolution during synthesis and under reaction conditions. Combining kinetic, transient and chemisorption analyses with modelling, we identify the acetylene adsorption energy as a speciation-sensitive activity descriptor, further determining the catalyst's selectivity with respect to coke formation.The stability of the different metal nanostructures is governed by the interplay between single atomsupport interaction and the chlorine affinity, promoting redispersion or agglomeration, respectively.
For decades, carbons have been the support of choice in acetylene hydrochlorination, a key industrial process for polyvinyl chloride manufacture. However, no unequivocal design criteria could be established to date, due to the complex interplay between the carbon host and the metal nanostructure. Herein, we disentangle the roles of carbon in determining activity and stability of platinum-, ruthenium-, and gold-based hydrochlorination catalysts and derive descriptors for optimal host design, by systematically varying the porous properties and surface functionalization of carbon, while preserving the active metal sites. The acetylene adsorption capacity is identified as central activity descriptor, while the density of acidic oxygen sites determines the coking tendency and thus catalyst stability. With this understanding, a platinum single-atom catalyst is developed with stable catalytic performance under two-fold accelerated deactivation conditions compared to the state-of-the-art system, marking a step ahead towards sustainable PVC production.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.