Selective hydrogenation of benzoic acid over bimetallic NiCo embedded in N‐doped carbon

Abstract

The selective hydrogenation of biomass‐derived benzoic acid (BA) to cyclohexane carboxylic acid (CCA) is vital to producing fine chemicals from renewable sources. Herein, a novel nitrogen‐doped carbon supported bimetallic catalyst (Ni1Co1/NC) was synthesized via a PVP‐assisted method to catalyze the selective hydrogenation of BA to CCA. Compared with the non‐doped Ni1Co1/C and single counterparts, Ni1Co1/NC exhibited a substantially enhanced activity, with 98.1% yield of CCA. The excellent performance was attributed to the NiCo synergistic effect and N‐doped thin carbon layer, which could increase the total proportion of Ni0 and Co0 species via donating electrons to Co and thus improve the H2 adsorption capacity, the hydrogenation activity of aromatic rings in BA and the stability. This work demonstrates a synergetic effect between NiCo bimetal and N‐doped thin carbon layer. This would pave the way for the rational design and synthesis of high‐performance non‐noble catalysts used in BA hydrogenation.

Noble‐Metal‐Free Carbon Encapsulated CoNi Alloy Catalyst for the Hydrogenation of 5‐(Hydroxymethyl) Furfural to Tetrahydrofurandiol in Aqueous Media

“…Similar results were obtained with the Co@C catalyst, which considerably promotes humins formation. These results show the positive effect of alloying between Co and Ni that contributes to the high activity and selectivity of Co 1 Ni 1 @C nanoparticles for the hydrogenation of HMF to BHMTHF previously observed in hydrogenation reactions [14,23,27,28] …”

“…Compared with samples of different Co/Ni ratios, the Co 1 Ni 1 sample exhibited the best activity, in good agreement with previously reported results where enhanced catalytic activity for hydrogenation reactions on Co 1 Ni 1 samples was found. [14,27,28] Moreover, we also checked the benefit of the presence of CoNi alloyed species in the Co 1 Ni 1 @C catalyst on the reaction performance, by carrying out the reaction using a carboncoated Ni and Co catalyst (Ni@C and Co@C) and a physical mixture of Co@C (50 %) and Ni@C (50 %) under optimal reaction conditions. As it is showed in Figure 9, conversion of HMF was not complete using the Ni@C catalyst, while selectivity to BHMTHF reached 87 %.…”

“…These results show the positive effect of alloying between Co and Ni that contributes to the high activity and selectivity of Co 1 Ni 1 @C nanoparticles for the hydrogenation of HMF to BHMTHF previously observed in hydrogenation reactions. [14,23,27,28] Finally, and from the point of view of a potential practical application of Co 1 Ni 1 @C catalyst for the production of BHMTHF from HMF, it is interesting to work at the highest HMF feed concentration, since it contributes to increase the productivity while reduce the purification cost. Therefore, we have studied the influence of the HMF concentration on the catalyst performance under optimized reaction conditions.…”

“…We have showed previously that these catalysts exhibited excellent activity and selectivity in a variety of hydrogenation reactions such as the chemoselective reduction of nitroarenes into anilines, reduction of levulinic acid into γvalerolactone, [23,26] hydrogenation of quinolines, [24] and reduction of HMF to 2,5-bis-(hydroxymethyl)furan, [13] and 3-(hydroxymethyl)cyclopentanone. [14] More recently, Yan et al [27] showed that NiCo bimetallic covered with a thin layer of Ndoped carbon (Ni 1 Co 1 /CN) synthesized by calcination of NiCo-MOF and PVP as the nitrogen precursor, exhibited excellent activity and selectivity in the hydrogenation of benzoic acid into cyclohexane carboxylic acid (98.1 % yield).…”

Selective Hydrogenation of N-Heterocyclic Carboxylate over Nitrogen-Doped Porous Carbon-Supported Nano-Ni

“…In recent years, for the high catalytic activity and mild hydrogenation conditions of N -heteroaromatic compounds, a series of homogeneous and heterogeneous noble metal-based catalysts such as Pd, Rh, Pt, Ir, and Ru have been synthesized and applied to various aromatic catalytic hydrogenation reactions. − In the homogeneous reaction system, the complexes formed by noble metals are used for the hydrogenation of N -heterocycles . Blaser et al used noble metal catalysts to study pyridine and its derivatives .…”