Pd embedded in porous carbon (Pd@CMK-3) as an active catalyst for Suzuki reactions: Accelerating mass transfer to enhance the reaction rate
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Shaoming Huang1(
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Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon (Pd@CMK-3) has been prepared by a strategy involving immersion, ammoniahydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd(0) and Pd(Ⅱ) species co-exist and were embedded in the matrix of the porous carbon (CMK-3). The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency (TOF) could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 ℃. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.
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Pd embedded in porous carbon (Pd@CMK-3) as an active catalyst for Suzuki reactions: Accelerating mass transfer to enhance the reaction rate
), Shaoming Huang1(
)
Abstract
Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon (Pd@CMK-3) has been prepared by a strategy involving immersion, ammoniahydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd(0) and Pd(Ⅱ) species co-exist and were embedded in the matrix of the porous carbon (CMK-3). The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency (TOF) could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 ℃. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.
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Acknowledgements
This work was supported by National Nature Science Foundation of China (NSFC) (Nos. 21101119 and 21173159), Nature Science Foundation of Zhejiang Province (NSFZJ) (No. LY14B010002), NSFC funds for Distinguished Young Scholars (No. 51025207), Science and Technology Department of Zhejiang Province (ZJSTD) Key Innovative Team (No. 2012R10014-10), and the Open Fund of the State Key Laboratory of Chemical Resource Engineering in Beijing University of Chemical Technology (No. CRE-2012-C-101).
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