Atomically dispersed Ni as the active site towards selective hydrogenation of nitroarenes. Issue 3 (25th January 2019)

• Record Type: Journal Article
• Authors: Yang, Fan; Wang, Minjian; Liu, Wei; Yang, Bin; Wang, Ying; Luo, Jun; Tang, Yushu; Hou, Liqiang; Li, Yun; Li, Zihui; Zhang, Bing; Yang, Wang; Li, Yongfeng
• Is Part Of: Green chemistry. Volume 21:Issue 3(2019)
• Page Start: 704
• Page End: 711
• Publication Date: 2019-01-25
• Subjects: Environmental chemistry -- Industrial applications -- Periodicals; Environmental management -- Periodicals; 660
• DOI: 10.1039/c8gc03664k
• Languages: English
• ISSNs: 1463-9262

Abstract

Abstract : Noble-metal-free catalytic hydrogenation of nitroarenes is achieved through the rational design of atomically dispersed Ni sites on N-doped porous carbon. The outstanding activity of the catalyst originates from the atomic dispersion of Ni active sites with a high Ni–N3 content. Abstract : Rational design of heterogeneous non-noble metal catalysts as highly efficient and selective catalysts for hydrogenation of nitroarenes with hydrogen as the reducing agent is currently a great challenge, which has attracted a great deal of attention. Herein, a new strategy for achieving atomic dispersion of Ni atoms on nitrogen-doped porous carbon (Ni–N–C) with a specific surface area of up to 810 m 2 g −1 and nickel loading as high as 4.4 wt% is developed, yielding high activity, chemoselectivity, and reusability of catalysts in the hydrogenation of nitroarenes using hydrogen as the reductant with a turnover of number (TON) value of 84 and a turnover of frequency (TOF) value of 8.4 h −1 for the first time. The Ni single atoms anchored on N-doped porous carbon by binding with nitrogen/carbon have been proved to be the active sites. Importantly, the Ni–N3 active species is found to contribute more activity compared with Ni–N2 and Ni–N4 . Density functional theory (DFT) calculations also reveal that the Ni–N3 structure exhibits the highest activity according to the lowest adsorption energy and the longest elongation N–O bonds of nitrobenzene, which originated from the induced charge transfer. This work opens a new route for rational design and accurate modulation of nanostructured organic molecular transformation catalysts at the atomic scale.