Cai Yutong, Zhang Yanan, Song Xiangen, Feng Siquan, Yuan Qiao, Li Xingju, Qiao Panzhe, Li Bin, Mu Jiali, Yan Li, Wu Xiao-Feng, Ding Yunjie
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning, 116023, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Small. 2024 Sep;20(37):e2401103. doi: 10.1002/smll.202401103. Epub 2024 May 6.
The unsaturated amides are traditionally synthesized by acylation of carboxylic acids or hydration of nitrile compounds but are rarely investigated by hydroaminocarbonylation of alkynes using heterogeneous single-metal-site catalysts (HSMSCs). Herein, single-Pd-site catalysts supported on N-doping carbon (NC) with different nitrogen dimensions inherited from corresponding metal-organic-framework precursors are successfully synthesized. 2D NC-supported single-Pd-site (Pd/NC-2D) exhibited the best performance with near 100% selectivity and 76% yield of acrylamide for acetylene hydroaminocarbonylation with better stability, superior to those of Pd/NC-3D, single-metal-site/nanoparticle coexisting catalyst, and nanoparticle catalyst. The coordination environment and molecular evolution of the single-Pd-site during the process of acetylene hydroaminocarbonylation on Pd/NC-2D are detailly illuminated by various characterizations and density functional theoretical calculations (DFT). DFT also showed the energy barrier of rate-determining step on Pd/NC-2D is lower than that of Pd/NC-3D. Furthermore, Pd/NC-2D catalyst illustrated the general applicability of the hydroaminocarbonylation for various alkynes.
不饱和酰胺传统上是通过羧酸的酰化反应或腈化合物的水合反应合成的，但很少使用多相单金属位点催化剂（HSMSCs）通过炔烃的氢胺羰基化反应进行研究。在此，成功合成了负载在具有不同氮维度的氮掺杂碳（NC）上的单钯位点催化剂，这些氮维度继承自相应的金属有机框架前驱体。二维NC负载的单钯位点（Pd/NC-2D）表现出最佳性能，在乙炔氢胺羰基化反应中丙烯酰胺的选择性接近100%，产率为76%，稳定性更好，优于Pd/NC-3D、单金属位点/纳米颗粒共存催化剂和纳米颗粒催化剂。通过各种表征和密度泛函理论计算（DFT）详细阐明了在Pd/NC-2D上乙炔氢胺羰基化过程中单钯位点的配位环境和分子演化。DFT还表明，Pd/NC-2D上速率决定步骤的能垒低于Pd/NC-3D。此外，Pd/NC-2D催化剂证明了氢胺羰基化反应对各种炔烃的普遍适用性。
