Structural Ni 0 -Ni δ+ Pair Sites for Highly Active Hydrogenation of Nitriles to Primary Amines

• Published in: Journal of the American Chemical Society 2024-08, Vol.146 (31), p.21623-21633
• Main Authors: Lyu, Kyeinfar, Jian, Xianfeng, Nie, Kaiqi, Liu, Shaoxiong, Huai, Mengjiao, Kang, Zhenyu, Liu, Dehuai, Lan, Xiaocheng, Wang, Tiefeng
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.4c05572

Supported metal pair sites have sparked interest due to their tremendous potential as bifunctional catalysts. Here, we report the structural Ni -Ni pair sites constructed in a well-defined nanocrystal phase of Ni P. These Ni -Ni pair sites exhibited a remarkable product formation rate of 123 mol /mol /h for the hydrogenation of benzonitrile (BN) to benzylamine (BA). The heterogeneity of surface Ni atoms over the Ni P crystal created two types of metal centers, Ni and Ni , with a specific spatial distance of 4-5 Å. The Ni site acted as the center for H activation, while the Ni site served as the adsorption and activation center for the C ≡ N group. The highly efficient cooperation effect of Ni -Ni pair sites resulted in a TOF of 2915 h in BN hydrogenation, which is 2.4 and 9.7 times higher than that over the mono-Ni and -Ni sites, respectively.