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

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.