Pd Nanoparticles Decorated by Oxidized Ru Clusters for Efficient C–H/C–H Coupling of Arenes

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2024-12-19 DOI:10.1021/acscatal.4c05551

Shingo Hasegawa, Shunta Tokutake, Koji Harano, Ken Motokura

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Abstract

Oxidative homocoupling of arenes is a challenging but attractive method for converting nonactivated aromatics into biaryl compounds. Applications and the mechanistic understanding of bimetallic nanocatalysts for arene C–H bond activation are limited at present. In this study, we found that a Pd–Ru bimetallic catalyst supported on Al₂O₃ showed remarkably high catalytic activity for the oxidative homocoupling of arenes owing to the synergistic effect between Pd and Ru. Structural analyses by high-angle annular dark-field scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and X-ray absorption spectroscopy revealed that the Pd nanoparticles were decorated by partially oxidized Ru clusters. Mechanistic studies indicated that the arene C–H bond cleavage was the rate-determining step and proceeded by a concerted metalation–deprotonation mechanism. It was proposed that the role of Ru is promoting the C–H activation step by generating electron-deficient Pd sites, which was supported by DFT calculations. The Ru-decorated Pd nanoparticles showed large turnover numbers for simple arenes.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.