Transfer Hydrogenation of Nitroarenes Catalyzed by CoCu Anchored on Nitrogen‐doped Porous Carbon

Abstract

The non‐precious metal catalysts with high catalytic activity is extremely desirable but still full of challenges. In this paper, CoCu bimetal immobilized on nitrogen‐doped porous carbon (CoCu‐N‐C) was prepared by an effective ligand‐stabilized pyrolysis strategy. CoCu‐N‐C exhibited excellent catalytic efficiency for the transfer hydrogenation of nitroarenes with ammonia borane as hydrogen source, which can be ascribed to the well dispersed metal nanoparticles, the synergetic interaction of CoCu bimetal and nitrogen‐doped carbon. The durability and recyclability experiments of the recycled CoCu‐N‐C catalyst indicated that no obvious change in catalytic performance was observed after five consecutive cycles. To gain insight into the catalytic mechanism of CoCu‐N‐C for the hydrogenation reaction, density functional theory calculations was also conducted. This work provides an universal approach for constructing highly efficient non‐precious metal heterogeneous catalysts and which may find diverse high performance applications.

Fast catalytic transfer hydrogenation of phenol to cyclohexanol over urea modified Ni@CN nanoparticles

“…33 Therefore, the electrons were redistributed on the surface of the catalyst, which is beneficial for improving the catalytic performance. 17,72–74…”

“…This implies that the doped N could help stabilize Ni nanoparticles and prevent their oxidation, which are beneficial for maintaining their high catalytic performance. 72 Moreover, compared with the Ni@C-450 sample, the Ni 0 peaks in Ni@CN-450 shifted to lower binding energy, which was caused by the electron transfer from N atoms to Ni. 33 Therefore, the electrons were redistributed on the surface of the catalyst, which is beneficial for improving the catalytic performance.…”

Highly efficient hydrogenation of nitroarenes by Co nanoparticles encapsulated in N-doped carbon nanotubes under mild conditions

“…12 Although the noble metal catalysts exhibit impressive catalytic performance, their high price and difficulty in separation from the reactants limited their large-scale industrial application. 13…”

“…12 Although the noble metal catalysts exhibit impressive catalytic performance, their high price and difficulty in separation from the reactants limited their large-scale industrial application. 13 There is a great need to design low cost, highly active, and stable multi-purpose non-noble metal catalysts, which is crucial for realizing the large-scale industrial production of aromatic amines. 14 Common non-precious metals used for the catalytic hydrogenation of aromatic nitro compounds includes Ni, 15 Co, 16 Cu, 17 and Fe.…”

Mild and Efficient Heterogeneous Hydrogenation of Nitroarenes Facilitated by a Pyrolytically Activated Dinuclear Ni(II)-Ce(III) Diimine Complex

“…Initial pertinent reports introduced cobalt(II) and iron(II) acetate-phenanthroline combinations for the creation of heterogeneous catalysts that enabled a convenient method for the syntheses of various organic amines [ 37 , 38 , 39 ]. Following these findings, a great deal of reports on the preparation of cobalt-based nanocomposites and their use in the reduction of nitroarenes either by H 2 gas or proper hydrogen transfer reagents (hydrazine, formic acid) have emerged [ 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 ]. It was established that the activity of these materials is heavily dependent on the nitrogen concentration [ 64 ] and, hence, the deployment of N-rich polydentate chelators is a promising means for the manufacture of empowered heterogeneous catalysts that are activated through annealing.…”