Nickel Carbide Nanoparticle Catalyst for Selective Hydrogenation of Nitriles to Primary Amines

Sho Yamaguchi; Daiki Kiyohira; Kohei Tada; Taiki Kawakami; Akira Miura; Takato Mitsudome; Tomoo Mizugaki

doi:10.1002/chem.202303573

Nickel Carbide Nanoparticle Catalyst for Selective Hydrogenation of Nitriles to Primary Amines

Chemistry. 2024 Mar 1;30(13):e202303573. doi: 10.1002/chem.202303573. Epub 2024 Jan 16.

Authors

Sho Yamaguchi^{1

2}, Daiki Kiyohira¹, Kohei Tada³, Taiki Kawakami¹, Akira Miura^{4

5}, Takato Mitsudome^{1

2

5}, Tomoo Mizugaki^{1

2

6}

Affiliations

¹ Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka, 565-0871, Japan.
³ Research Institute of Electrochemical Energy (RIECEN), Department of Energy and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka, 563-8577, Japan.
⁴ Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Sapporo, Hokkaido, 060-8628, Japan.
⁵ PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama, 333-0012, Japan.
⁶ Research Center for Solar Energy Chemistry, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan.

PMID: 38179895
DOI: 10.1002/chem.202303573

Abstract

Despite its unique physicochemical properties, the catalytic application of nickel carbide (Ni₃ C) in organic synthesis is rare. In this study, we report well-defined nanocrystalline Ni₃ C (nano-Ni₃ C) as a highly active catalyst for the selective hydrogenation of nitriles to primary amines. The activity of the aluminum-oxide-supported nano-Ni₃ C (nano-Ni₃ C/Al₂ O₃ ) catalyst surpasses that of Ni nanoparticles. Various aromatic and aliphatic nitriles and dinitriles were successfully converted to the corresponding primary amines under mild conditions (1 bar H₂ pressure). Furthermore, the nano-Ni₃ C/Al₂ O₃ catalyst was reusable and applicable to gram-scale experiments. Density functional theory calculations suggest the formation of polar hydrogen species on the nano-Ni₃ C surface, which were attributed to the high activity of nano-Ni₃ C towards nitrile hydrogenation. This study demonstrates the utility of metal carbides as a new class of catalysts for liquid-phase organic reactions.

Keywords: amine; heterogeneous catalyst; hydrogenation; nickel carbide; nitrile.

Abstract

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