Issue 26, 2020

A cobalt phosphide catalyst for the hydrogenation of nitriles

Abstract

The study of metal phosphide catalysts for organic synthesis is rare. We present, for the first time, a well-defined nano-cobalt phosphide (nano-Co2P) that can serve as a new class of catalysts for the hydrogenation of nitriles to primary amines. While earth-abundant metal catalysts for nitrile hydrogenation generally suffer from air-instability (pyrophoricity), low activity and the need for harsh reaction conditions, nano-Co2P shows both air-stability and remarkably high activity for the hydrogenation of valeronitrile with an excellent turnover number exceeding 58000, which is over 20- to 500-fold greater than that of those previously reported. Moreover, nano-Co2P efficiently promotes the hydrogenation of a wide range of nitriles, which include di- and tetra-nitriles, to the corresponding primary amines even under just 1 bar of H2 pressure, far milder than the conventional reaction conditions. Detailed spectroscopic studies reveal that the high performance of nano-Co2P is attributed to its air-stable metallic nature and the increase of the d-electron density of Co near the Fermi level by the phosphidation of Co, which thus leads to the accelerated activation of both nitrile and H2. Such a phosphidation provides a promising method for the design of an advanced catalyst with high activity and stability in highly efficient and environmentally benign hydrogenations.

Graphical abstract: A cobalt phosphide catalyst for the hydrogenation of nitriles

Supplementary files

Article information

Article type
Edge Article
Submitted
14 Jan 2020
Accepted
04 Jun 2020
First published
09 Jun 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 6682-6689

A cobalt phosphide catalyst for the hydrogenation of nitriles

T. Mitsudome, M. Sheng, A. Nakata, J. Yamasaki, T. Mizugaki and K. Jitsukawa, Chem. Sci., 2020, 11, 6682 DOI: 10.1039/D0SC00247J

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