Programmable Pd‐N Engineering of Mesoporous Carbon Synthesized by Multicomponent Polymerization‐Assembly Strategy for Efficient Alkynol Semihydrogenation

Abstract Multicomponent polymerization is an attractive route to synthesize various polymers with complicated structures and holds promise for the construction of functional porous carbons with well‐defined microstructures. However, the process faces challenges in monomers’ distinct properties affecting co‐dissolution, interaction regulation with porogens, mesostructure retention of carbon materials. Here, a multicomponent polymerization‐assembly strategy is proposed to synthesize mesoporous poly(aniline‐co‐pyrrole‐co‐diaminopyridine) (PAPD) and its derived carbon (PAPD‐C). Adjusting the monomer feed ratio can achieve more precise regulation of nitrogen species than traditional synthesis methods, which facilitates the modulation of Pd surface electrons. As a result, the mesoporous Pd/PAPD1‐C catalyst achieves 99% conversion and 97% selectivity in the semihydrogenation of 2‐methyl‐3‐butyn‐2‐ol. Density functional theory calculations reveal that equal amounts of pyridinic N and pyrrolic N provide a favorable microenvironment for active Pd sites, thereby reducing the energy barrier and accelerating the reaction process. This work provides new insights into the synthesis of modified porous carbons and the performance optimization of metal/carbon‐based catalysts by fine‐tuning of heteroatom configurations.