Tailoring a Dynamic Metal–Polymer Interaction to Improve Catalyst Selectivity and Longevity in Hydrogenation

• Published in: Angewandte Chemie Vol. 133; no. 22; pp. 12590 - 12597
• Main Authors: Hyun, Kyunglim, Park, Younghwan, Lee, Songhyun, Lee, Jueun, Choi, Yeonwoo, Shin, Seung‐Jae, Kim, Hyungjun, Choi, Minkee
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 25.05.2021
• Subjects: Acetylene; Catalysts; Chemical synthesis; Chemistry; Deactivation; DMPI; Hydrogenation; Metals; metal–support interactions; Palladium; partial hydrogenation; Polymers; Selectivity; Tuning
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202100814

Controlling metal–support interactions is important for tuning the catalytic properties of supported metal catalysts. Here, premade Pd particles are supported on stable polymers containing different ligating functionalities to control the metal–polymer interactions and their catalytic properties in industrially relevant acetylene partial hydrogenation. The polymers containing strongly ligating groups (e.g., Ar‐SH and Ar‐S‐Ar) can form a polymer overlayer on the Pd surface, which enables selective acetylene adsorption and partial hydrogenation to ethylene without deactivation. In contrast, polymers with weakly ligating groups (e.g., Ar‐O‐Ar) do not form an overlayer, resulting in non‐selective hydrogenation and fast deactivation, similar to Pd catalysts on conventional inorganic supports. The results imply that tuning the metal–polymer interactions via rational polymer design can provide an efficient way of synthesizing selective and stable catalysts for hydrogenation. We synthesized a series of polymers with similar framework structures but different metal‐ligating functionalities as supports for Pd catalysts to control the dynamic metal–polymer interactions (DMPI) and catalytic properties. The polymers containing strongly ligating groups can form a polymer overlayer on the Pd surface via DMPI, which enables selective acetylene adsorption and partial hydrogenation to ethylene without deactivation.