Doped activated carbons obtained from nitrogen and sulfur-containing polymers as metal-free catalysts for application in nitroarenes hydrogenation

Villora-Picó, Juan-José; Gil-Muñoz, Gema; Sepúlveda-Escribano, Antonio; Pastor-Blas, M. Mercedes

doi:10.1016/j.ijhydene.2023.12.005

Cited by 3 publications

(3 citation statements)

References 85 publications

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“…These samples showed mainly pyridinic and pyrrolic species. Nevertheless, our previous studies using metal-free N-doped carbons obtained from polymers showed that the most effective catalysts contained quaternary N functionalities [ 55 ]. This leads to the conclusion that more research work is needed to clarify the precise role of nitrogen functionalities in the selective hydrogenation of nitroarenes to the corresponding anilines.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, we explored an alternative synthesis strategy based on one-step carbonization and N doping using nitrogen-rich carbon precursors. Instead of our first approach based on the polymerization of pyrrole or aniline monomers on the surface of the activated porous carbon, we synthesized polypyrrole and polyaniline and used the N-rich polymers not only as source of N but also as carbon precursors [ 52 , 55 ]. An adequate control of the experimental variables during the oxidative chemical polymerization of the monomers in aqueous media permitted the tailoring of the structure of the polymeric chain to enhance a homogeneous distribution of nitrogen functionalities, which served as catalytic sites in both the bulk and the carbon surface.…”

Section: Introductionmentioning

confidence: 99%

“…Steam activation at 900 °C resulted in an important increase in the surface area and pore development of the polymer-derived carbons, but in turn, considerable decomposition of nitrogen functionalities was produced [ 52 ]. Activation treatments require an exhaustive control of time and temperature specifically selected for each carbon material in order to ensure an adequate compromise between well-developed textural properties (surface area, pore volume and pore distribution) and doping degree [ 55 ]. It has been reported that in situ doping of the carbon framework tends to form pyrrolic and/or pyridinic N atoms, while graphitic N is normally generated after a high-temperature post-treatment [ 56 ].…”

Section: Introductionmentioning

confidence: 99%

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Design and Synthesis of N-Doped Carbons as Efficient Metal-Free Catalysts in the Hydrogenation of 1-Chloro-4-Nitrobenzene

Villora-Picó,

Sepúlveda-Escribano,

Pastor-Blas

2024

IJMS

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Metal-free catalysts based on nitrogen-doped porous carbons were designed and synthesized from mixtures of melamine as nitrogen and carbon sources and calcium citrate as carbon source and porogen system. Considering the physicochemical and textural properties of the prepared carbons, a melamine/citrate ratio of 2:1 was selected to study the effect of the pyrolysis temperature. It was observed that a minimum pyrolysis temperature of 750 °C is required to obtain a carbonaceous structure. However, although there is a decrease in the nitrogen amount at higher pyrolysis temperatures, a gradual development of the porosity is produced from 750 °C to 850 °C. Above that temperature, a deterioration of the carbon porous structure is produced. All the prepared carbon materials, with no need for a further activation treatment, were active in the hydrogenation reaction of 1-chloro-4-nitrobenzene. A full degree of conversion was reached with the most active catalysts obtained from 2:1 melamine/citrate mixtures pyrolyzed at 850 °C and 900 °C, which exhibited a suitable compromise between the N-doping level and developed mesoporosity that facilitates the access of the reactants to the catalytic sites. What is more, all the materials showed 100% selectivity for the hydrogenation of the nitro group to form the corresponding chloro-aniline.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Design and Synthesis of N-Doped Carbons as Efficient Metal-Free Catalysts in the Hydrogenation of 1-Chloro-4-Nitrobenzene

Villora-Picó,

Sepúlveda-Escribano,

Pastor-Blas

2024

IJMS

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Highly active iron oxide@N catalyst derived from the iron acetate/polyacrylonitrile threads: Driving nitroarene conversion to value‐added amines

Rubab,

Sharif,

Razzaq

et al. 2024

J of Applied Polymer Sci

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Chemoselective reduction of nitroarenes to corresponding arylamines is a significant reaction in the chemical industry. However, in the presence of other reducible groups, including halogenated nitrobenzene, nitrobiphenyl, and nitroquinoline in the same molecule of nitroaromatics, the control of chemoselectivity remains challenging. Here, a facile fabrication of a heterogeneous iron‐based catalyst is reported as a potential alternative to precious metal catalysts for the chemoselective reduction of nitroarenes. The pyrolysis of iron acetate/polyacrylonitrile (PAN) template under an inert atmosphere furnishes active Fe3O4 nanoparticles (NPs) encapsulated in nitrogen‐doped (N‐doped) carbon layers, which can provide more catalytic active sites (Fe3O4/PAN@800). Notably, non‐precious iron oxide NPs supported on N‐doped carbon support prevent aggregation, thereby enhancing the catalytic activity. The sustainable and reusable Fe3O4/PAN@800 catalyst, having only 0.8% metal content as demonstrated by x‐ray photoelectron spectroscopy, delivers excellent yields of corresponding amines from differently functionalized nitroarenes. Hydrogenation of a series of structurally functionalized nitroarenes produced excellent yields of anilines, which serve as building blocks and intermediates for fine and bulk chemicals. Hydrogenation of 2‐chloro‐3‐nitropyridine, 2‐nitro‐1,1′‐biphenyl, ortho‐nitroaniline, and 4‐aminophenyl acrylonitrile yielded respective anilines up to 99%. The active sites of Fe3O4 have magnetic performance, hence, the catalyst can be easily recovered using a magnet and reused for at least five cycles without significant loss of catalytic activity. Therefore, the easily prepared, cost‐effective, and reusable Fe3O4/PAN@800 catalyst presented in this study shows potential for applications in the selective reduction of aromatic nitro compounds. Consequently, this study potentially establishes a guideline for the facile preparation of abundant transition‐non‐noble metal‐based reusable supported catalysts for various applications in the chemical industry.

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N-doped activated carbons obtained from polyaniline for toluene and water adsorption

Villora-Picó,

Coloma-Pascual,

Sepúlveda-Escribano

et al. 2024

Inorganic Chemistry Communications

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Doped activated carbons obtained from nitrogen and sulfur-containing polymers as metal-free catalysts for application in nitroarenes hydrogenation

Cited by 3 publications

References 85 publications

Design and Synthesis of N-Doped Carbons as Efficient Metal-Free Catalysts in the Hydrogenation of 1-Chloro-4-Nitrobenzene

Design and Synthesis of N-Doped Carbons as Efficient Metal-Free Catalysts in the Hydrogenation of 1-Chloro-4-Nitrobenzene

Highly active iron oxide@N catalyst derived from the iron acetate/polyacrylonitrile threads: Driving nitroarene conversion to value‐added amines

N-doped activated carbons obtained from polyaniline for toluene and water adsorption

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