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通过调控Pd/MOF界面电子转移促进Pd纳米颗粒的光催化铃木偶联反应

Boosting photocatalytic Suzuki coupling reaction over Pd nanoparticles by regulating Pd/MOF interfacial electron transfer

  • 摘要: 钯(Pd)催化的碳-碳键偶联反应具有很重要的意义,但是其通常需要较为苛刻的条件。本文报道了利用一种金属有机框架(MOF),ZIF-8,来负载钯纳米颗粒用于界面调控的光催化铃木偶联(Suzuki coupling)反应。两种合成的Pd/MOFs催化剂分别命名为PdPVP/ZIF-8和Pd/ZIF-8,它们具有相似的钯纳米颗粒的尺寸和载量,区别在于前者有聚乙烯吡咯烷酮(PVP)作为表面活性剂。通过一氧化碳吸附的傅里叶变换漫反射红外光谱(CO-DRIFT),可以证明Pd/ZIF-8比PdPVP/ZIF-8的钯纳米颗粒具有更负的电子态。在光催化碘苯和苯硼酸的铃木偶联反应中,Pd/ZIF-8具有更高的活性(产率99.1%),优于PdPVP/ZIF-8(产率57.9%),此外,Pd/ZIF-8展示出良好的稳定性和很好的底物适用范围。Pd/ZIF-8更高的活性可以通过MOF和钯纳米颗粒在没有表面活性剂的界面更好的电子传递解释。本工作将光催化和界面电子转移结合,为钯催化的碳-碳键偶联反应提供了新的思路。

     

    Abstract: Palladium-catalyzed C-C coupling reactions are of significant importance, but they often require harsh conditions. Herein, we report an interface-regulated photocatalytic Suzuki coupling reaction over Pd nanoparticles supported on a metal-organic framework (MOF), ZIF-8. Two Pd/MOFs were synthesized, PdPVP/ZIF-8 and Pd/ZIF-8, which have similar Pd sizes and loading amounts, except that the former contains poly(vinylpyrrolidone) (PVP) as a surfactant. The diffuse-reflectance infrared Fourier transform of CO adsorption (CO-DRIFT) indicates that Pd/ZIF-8 represents a more negative electronic state of Pd than PdPVP/ZIF-8. In the photocatalytic Suzuki coupling reaction between iodobenzene and phenylboronic acid, Pd/ZIF-8 exhibits excellent performance (99.1% yield), much better than that of PdPVP/ZIF-8 (57.9% yield). Moreover, Pd/ZIF-8 is highly stable and shows broad substrate scope for this reaction. The superior activity of Pd/ZIF-8 can be attributed to sufficient electron transfer between the MOFs and Pd nanoparticles in the absence of an interfacial surfactant. This work provides new insights into a Pd-catalyzed C-C coupling reaction involving photocatalysis and interfacial electron transfer.

     

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