Nickel nanoparticle/carbon catalysts derived from a novel aqueous-synthesized metal-organic framework for nitroarene reduction

Abstract

Carbon-supported, non-noble metal-based catalysts derived from metal-organic frameworks (MOFs) are attractive alternatives to noble metal-based systems, but typical syntheses of the starting MOFs are not desirable from an environmental and practical perspective (e.g., they rely on non-innocuous organic solvents and long reaction times). Here, we report the preparation of a Ni-based MOF in aqueous medium, at moderate temperature (95 °C) and in a short reaction time (<30 min), which was used as a sacrificial template to access a family of Ni nanoparticle/carbon hybrids that were then tested as catalysts in the reduction of 4-nitrophenol (4-NP). The MOF-derived hybrids exhibited a mesoporous texture, with specific surface areas between 250 and 450 m2 g−1 depending on the carbonization temperature applied to the MOF, as well as high Ni contents (between 36 and 57 wt%). Notwithstanding the latter, the metal was homogeneously distributed throughout the carbon matrix in the hybrid and was quite resistant to extensive agglomeration and sintering, even at temperatures as high as 1000 °C. With increasing carbonization temperature, the Ni component was seen to go through different crystal phases, i.e., Ni3C phase Ni hexagonal close-packed phase Ni face-centered cubic phase. The results of the catalytic tests suggested the former and latter phases to be the most active towards the reduction of 4-NP, with catalytic activity values as high as 0.039 mol4-NP molNi−1 min−1.