Molecule Saturation Boosts Acetylene Semihydrogenation Activity and Selectivity on a Core‐Shell Ruthenium@Palladium Catalyst

• Published in: Angewandte Chemie International Edition Vol. 62; no. 23; pp. e202300110 - n/a
• Main Authors: Zhu, Chuwei, Xu, Wenlong, Liu, Fang, Luo, Jie, Lu, Junling, Li, Wei‐Xue
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 05.06.2023
• Edition: International ed. in English
• Subjects: Acetylene; Adsorption; Atomic Layer Deposition; Catalysis; Catalysts; Coordination; First-Principles Calculations; Molecular structure; Molecule Saturation; Palladium; Ruthenium; Semihydrogenation of Acetylene; Sensitivity; Strained Bimetallic Overlayer; Molecule Saturation; Strained Bimetallic Overlayer; First-Principles Calculations; Atomic Layer Deposition; Semihydrogenation of Acetylene
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202300110

Increasing selectivity without the expense of activity is desired but challenging in heterogeneous catalysis. By revealing the molecule saturation and adsorption sensitivity on overlayer thickness, strain, and coordination of Pd‐based catalysts from first‐principles calculations, we designed a stable Pd monolayer (ML) catalyst on a Ru terrace to boost both activity and selectivity of acetylene semihydrogenation. The least saturated molecule is most sensitive to the change in catalyst electronic and geometric properties. By simultaneously compressing the Pd ML and exposing the high coordination sites, the adsorption of more saturated ethylene is considerably weakened to facilitate the desorption for high selectivity. The even stronger weakening to the least saturated acetylene drives its hydrogenation such that it is more exothermic, thereby boosting the activity. Tailoring the molecule saturation and its sensitivity to structure and composition provides a tool for rational design of efficient catalysts. An effective catalyst for semihydrogenation of acetylene was created by layering Pd on large Ru nanoparticles with terrace sites and a smaller lattice constant. The catalyst stabilizes unsaturated acetylene as it undergoes semihydrogenation while promoting ethylene desorption, thereby achieving high activity and selectivity at the same time.