Metal–Organic Framework Mediated Cobalt/Nitrogen‐Doped Carbon Hybrids as Efficient and Chemoselective Catalysts for the Hydrogenation of Nitroarenes

Abstract

A Co@N‐doped carbon (Co@NC) hybrid was synthesized by thermal decomposition of the metal–organic framework (MOF) ZIF‐67 under N2 atmosphere. These hybrid materials exhibit outstanding catalytic activity and chemoselectivity for the conversion of a wide range of substituted nitroarenes to their corresponding anilines under relatively mild reaction conditions. The high catalytic performance is attributed to the formation of cobalt nanoparticles and to the presence of atomically dispersed Co species in close interaction with nitrogen‐doped graphene. Both active species are formed in situ during the pyrolytic transformation of ZIF‐67. The catalysts could be reused in consecutive runs, exhibiting a slightly lower activity ascribed to blockage of the active sites by strongly adsorbed reaction species. These results open up a pathway for the design of noble‐metal‐free solid catalysts for industrial applications.

Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes

“…Recently, tremendous efforts have led to the development of cheaper first-row transitionmetal-based hydrogenation catalysts (i.e. Fe, Co, and Ni) [15,[29][30][31][32][33][34][35][36][37][38][39][40][41]. Among these catalysts, N-doped carbon supported cobalt materials prepared by the carbonization of metal-organicframeworks (MOFs) or a mixture of cobalt salts and organic complex exhibited good activity and chemoselectivity in the hydrogenation of nitroarenes [29-32, 36, 39-46].…”

Preparation and Performances of ZIF-67-Derived FeCo Bimetallic Catalysts for CO2 Hydrogenation to Light Olefins

“…To study the relationship between the degree of graphitization and the calcination temperature, FeCo/NC-T was analyzed by Raman spectra as displayed in Figure 7a. The D-band at 1345 cm −1 and the G-band at 1580 cm −1 were observed, attributed to disordered carbon and graphitic carbon [58]. To observe the distribution of element species in detail, high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and EDS element mapping was used to analyze FeCo/NC-600.…”

“…To study the relationship between the degree of graphitization and the calcination temperature, FeCo/NC-T was analyzed by Raman spectra as displayed in Figure 7a. The D-band at 1345 cm −1 and the G-band at 1580 cm −1 were observed, attributed to disordered carbon and graphitic carbon [58]. To study the relationship between the degree of graphitization and the calcination temperature, FeCo/NC-T was analyzed by Raman spectra as displayed in Figure 7a.…”

Metal–organic framework‐derived cobalt and nitrogen co‐doped porous carbon with four‐coordinated Co–Nx for efficient acetylene hydrochlorination

“…It can be seen from the spectra that the proportion of metallic Co increases from ZIF15C to ZIF5C as Co addition increases, but it decreases in ZIF‐67C due to the easy acid etching for large‐sized Co particles. The unfitted spectra in the range of 784–790 eV can be assigned to satellite peaks, which usually appear accompanying CoO x . The relative contents and binding energies of various cobalt species are presented in Table .…”