A Hierarchical-Structured Impeller with Engineered Pd Nanoparticles Catalyzing Suzuki Coupling Reactions for High-Purity Biphenyl

Abstract

Suzuki cross-coupling reactions catalyzed by palladium are authoritative protocols in fine-chemical synthesis. Mass transfer and catalyst activity are both significant factors affecting the reaction efficiency in heterogeneous reactions. Although the holistic catalysts hold great promise in heterogeneous reactions due to the enhanced mass transport and convenient recycling, the unsatisfied catalytic activity has impeded further large-scale applications. In addition, another pronounced barrier is the product separation in the intricate system. Here, the catalytic production and separation of biphenyl (purity of 99.7%) were achieved by integrating the Suzuki cross-coupling reactions and the crystallization separation for the first time. A hierarchical-structured impeller with Pd nanoparticles (NPs) loaded on the Ni­(OH)2 nanosheets was prepared to catalyze the Suzuki reactions for bromobenzene, which exhibits a high turnover frequency (TOF) value of 25,976 h–1 and a yield of 99.5%. The X-ray absorption fine structure (XAFS) analysis has unveiled that the electron transfer between the Pd NPs and Ni­(OH)2 accounts for the greatly enhanced catalytic activity. The findings inspire new insights toward rational engineering of highly efficient holistic catalysts for Suzuki reaction, and the innovative integrated technology offers an avenue for the separation and collection of products.

Pd/Mg(OH)2/MgO–ZrO2 Nanocomposite Systems for Highly Efficient Suzuki–Miyaura Coupling Reaction at Room Temperature: Implications for Low-Carbon Green Organic Synthesis

“…Figure S10 shows the linear plots of ln­( C 0 / C t ) against reaction time under different temperatures and the corresponding Arrhenius plots. After calculation, the apparent activation energies ( E a ) for Ph–Br and Ph–Cl are 9.0 and 16.37 kJ mol –1 , respectively, which are much lower than the values we reported before (Figure d). The performance of Pd/MZ-0.25 was also compared with some recently reported Pd-supported catalysts for the coupling of Ph–Br or Ph–Cl with phenylboronic acid.…”

“…(c) Conversion curves of Ph–Cl were catalyzed by Pd/MZ-0.25 at different temperatures. (d) E a of Ph–Br and Ph–Cl catalyzed by Pd/MZ-0.25 and comparison with that catalyzed by Pd/Ni­(OH) 2 /SS that we reported before.…”

Copper-Based Integral Catalytic Impeller for the Rapid Catalytic Reduction of 4-Nitrophenol

“…Sandee et al constructed a mechanical stirrer with hydroformylation catalyst-anchored monoliths as the blades, which shows effectiveness in the hydroformylation of both higher and lower alkenes. Our group has also developed a series of integrated catalytic agitators with a specific structure and catalytic species, including Fe-AI, , Ag-AI, and Pd-AI, which exhibit high catalytic activity for 4-NP reduction, Fenton reaction, Suzuki coupling reaction, etc., and feature great separation and recycling stability. If copper nanoparticles can be directly modified onto the blades of AI, then high catalytic activity and rapid separation are possible to be achieved simultaneously.…”

Proof of Concept: Interface of Recyclable Organogels with Embedded Palladium Nanoparticles Catalyzing Suzuki–Miyaura Coupling in Water at Room Temperature

“…On completion of the cross-coupling reactions, the aqueous layer above the gel can simply decant and the intact gel is reusable for multiple cycles (Figure a). We have opted for Suzuki–Miyaura coupling − (Figure b) for this purpose. First Suzuki–Miyaura cross-coupling reaction between 4-bromobenzoic acid and phenylboronic acid was performed to test the catalytic performance of the Pd-embedded peptide-based hybrid gel.…”