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A cobalt phosphide catalyst for the hydrogenation of nitriles.
Chemical Science ( IF 8.4 ) Pub Date : 2020-06-09 , DOI: 10.1039/d0sc00247j
Takato Mitsudome 1 , Min Sheng 1 , Ayako Nakata 2 , Jun Yamasaki 3 , Tomoo Mizugaki 1 , Koichiro Jitsukawa 1
Affiliation  

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.

中文翻译:

用于腈加氢的磷化钴催化剂。

用于有机合成的金属磷化物催化剂的研究很少。我们首次提出了一种定义明确的纳米钴磷化物 (nano-Co 2 P),它可以作为一种新型催化剂,用于将腈类氢化成伯胺。虽然用于腈加氢的地球上丰富的金属催化剂通常具有空气不稳定性(自燃性)、低活性和需要苛刻的反应条件,但 nano-Co 2 P 显示出空气稳定性和非常高的戊腈加氢活性。优秀的营业额超过 58000,比之前报道的高出 20 到 500 倍以上。此外,纳米Co 2即使在仅 1 bar 的 H 2压力下, P 也能有效地促进多种腈(包括二腈和四腈)氢化成相应的伯胺,远比常规反应条件温和。详细的光谱研究表明,纳米 Co 2 P的高性能归因于其空气稳定的金属性质,以及通过钴的磷化作用使 Co 在费米能级附近的 d 电子密度增加,从而导致加速腈和H 2的活化。这种磷化为设计在高效和环境友好的氢化中具有高活性和稳定性的先进催化剂提供了一种有前景的方法。
更新日期:2020-07-08
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