Single‐Pd‐Site Catalyst Induced by Different Dimensional Nitrogen of N‐Doping Carbon for Efficient Hydroaminocarbonylation of Alkynes

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-09, Vol.20 (37), p.e2401103-n/a
• Main Authors: 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
• Format: Article
• Language: English
• Subjects: Acetylene; Acrylamide; Acylation; Alkynes; alkynes hydroaminocarbonylation; Amides; Carbon; Carboxylic acids; Catalysts; Chemical synthesis; coordination environment; Density functional theory; different dimensional; Doping; Nanoparticles; Nitrogen; N‐doping carbon; Palladium; single‐Pd‐site catalysts
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202401103

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 (Pd1/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 Pd1/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 Pd1/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 Pd1/NC‐2D is lower than that of Pd1/NC‐3D. Furthermore, Pd1/NC‐2D catalyst illustrated the general applicability of the hydroaminocarbonylation for various alkynes. Heterogeneous single‐Pd‐site catalysts with special coordination environments induced by different dimensional nitrogen of N‐doping carbon materials are successfully synthesized. Pd1/NC‐2D with a beneficial coordination structure exhibited the best performance, superior to those of Pd1/NC‐3D, single‐metal‐site/nanoparticle coexisting catalyst, and pure nanoparticle catalyst.