Template‐Oriented Polyaniline‐Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives

Developing well-defined structures and desired properties for porous organic polymer (POP) supported catalysts by controlling their composition, size, and morphology is of great significance. Herein, we report a preparation of polyaniline (PANI) supported Pd nanoparticles (NPs) with controllable structure and morphology. The protocol involves the introduction of MnO₂ with different crystal structures (α, β, γ, δ, ϵ) serving as both the reaction template and the oxidant. The different forms of MnO₂ each convert aniline to a PANI that contains a unique regular distribution of benzene and quinone. This leads to the Pd/PANI catalysts with different charge transfer properties between Pd and PANI, as well as different dispersions of the metal NPs. In this case, the Pd/ϵ-PANI catalyst greatly improves the turnover frequency (TOF; to 88.3 h^-1 ), in the reductive coupling of furfural derivatives to potential bio-based plasticizers. Systematic characterizations reveal the unique oxidation state of the support in the Pd/ϵ-PANI catalyst and coordination mode of Pd that drives the formation of highly dispersed Pd nanoclusters. Density functional theory (DFT) calculations show the more electron rich Pd/PANI catalyst has the lower energy barrier in the oxidative addition step, which favors the C-C coupling reaction.