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

Yutong Cai; Yanan Zhang; Xiangen Song; Siquan Feng; Qiao Yuan; Xingju Li; Panzhe Qiao; Bin Li; Jiali Mu; Li Yan; Xiao-Feng Wu; Yunjie Ding

doi:10.1002/smll.202401103

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

Small. 2024 May 6:e2401103. doi: 10.1002/smll.202401103. Online ahead of print.

Authors

Yutong Cai^{1

2}, Yanan Zhang^{2

3}, Xiangen Song¹, Siquan Feng¹, Qiao Yuan^{1

2}, Xingju Li¹, Panzhe Qiao⁴, Bin Li^{1

2}, Jiali Mu¹, Li Yan¹, Xiao-Feng Wu^{1

2

5}, Yunjie Ding^{1

2

6}

Affiliations

¹ Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning, 116023, China.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning, 116023, China.
⁴ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, China.
⁵ Leibniz-Institut für Katalyse e. V., Albert-Einstein-Straβe 29a, 18059, Rostock, Germany.
⁶ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning, 116023, China.

PMID: 38709231
DOI: 10.1002/smll.202401103

Abstract

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.

Keywords: N‐doping carbon; alkynes hydroaminocarbonylation; coordination environment; different dimensional; single‐Pd‐site catalysts.

Abstract

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