Citation:
Zhe Chen, Yu Liang, Da-Shuang Jia, Zhi-Min Cui, Wei-Guo Song. Simple synthesis of sub-nanometer Pd clusters: High catalytic activity of Pd/PEG-PNIPAM in Suzuki reaction[J]. Chinese Journal of Catalysis,
;2017, 38(4): 651-657.
doi:
10.1016/S1872-2067(17)62797-9
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Ultra-small metal nanoclusters have high surface energy and abundant active sites, and therefore their catalytic activities are usually significantly higher than those of larger nanoparticles. A temperature-responsive copolymer, namely poly(ethylene glycol)-co-poly(N-isopropylacrylamide) (PEG-PNIPAM) was synthesized as the first step, and then ultra-small Pd clusters stabilized within PEG-PNIPAM copolymer micelles were formed by direct reduction. Pd nanoclusters of size less than 2 nm showed outstanding catalytic activity in the Suzuki coupling reaction. The reaction between iodobenzene and phenylboronic acid was completed in as little as 10 s (turnover frequency=4.3×104 h-1). A yield of 64% was achieved in 5 min in the reaction between chlorobenzene and phenylboronic acid. The catalyst showed significant deactivation during three consecutive runs. However, this composite catalyst consisting of Pd/PEG-PNIPAM can be easily recycled based on the reversible phase transition of temperature-responsive PEG-PNIPAM. This catalyst therefore has good potential for practical applications.
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