Iron Pyrite Nanocrystals: A Potential Catalyst for Selective Transfer Hydrogenation of Functionalized Nitroarenes

Adhikari, Menuka; Singh, Anuradha; Echeverría, Elena; McIlroy, David N.; Vasquez, Yolanda

doi:10.1021/acsomega.0c01637

Cited by 12 publications

(15 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…β-FeOOH nanoneedles were synthesized using poly(ethyleneimine) (PEI) (MW = 750,000) as a surface capping agent and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). 1 , 7 , 46 PEI is a positively charged ligand that remains protonated in solution and limits unidirectional growth because it adsorbs onto the (200) planes of β-FeOOH nanoneedles. 1 , 7 , 47 , 48 Consistent with previous reports, higher concentrations of PEI yielded shorter nanoneedles.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Magnetite Nanorods from the Reduction of Iron Oxy-Hydroxide with Hydrazine

et al. 2020

Self Cite

View full text Add to dashboard Cite

Nanowires and nanorods of magnetite (Fe 3 O 4 ) are of interest due to their varied biological applications but most importantly for their use as magnetic resonance imaging contrast agents. One-dimensional (1D) structures of magnetite, however, are more challenging to synthesize because the surface energy favors the formation of isotropic structures. Synthetic protocols can be dichotomous, producing either the 1D structure or the magnetite phase but not both. Here, superparamagnetic Fe 3 O 4 nanorods were prepared in solution by the reduction of iron oxy-hydroxide (β-FeOOH) nanoneedles with hydrazine (N 2 H 4 ). The amount of hydrazine and the reaction time affected the phase and morphology of the resulting iron oxide nanoparticles. One-dimensional nanostructures of Fe 3 O 4 could be produced consistently from various aspect ratios of β-FeOOH nanoneedles, although the length of the template was not retained. Fe 3 O 4 nanorods were characterized by transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and SQUID magnetometry.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of Magnetite Nanorods from the Reduction of Iron Oxy-Hydroxide with Hydrazine

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…In the case of the halogen-substituted nitroarenes, the absence of any dehalogenated product demonstrates the potential of the Au/MgO catalyst unlike palladium and platinum catalysts, which are prone to dehalogenation and poisoning of the metal by strong adsorption of the formed halogen. 50 The slightly higher reaction time for conversion of ortho-substituted nitroarenes compared to the para-substituted ones indicated a steric effect. For the reusability of the catalyst, it was separated from the reaction mixture and washed with water followed by acetone and then dried at 60 °C to be reused in the next reaction cycle.…”

Section: ■ Results and Discussionmentioning

confidence: 84%

“…This could be due to the formation of nitrophenolate ions from 4-nitrophenol enabling better solubility in water and diffusion of the reactant. In the case of the halogen-substituted nitroarenes, the absence of any dehalogenated product demonstrates the potential of the Au/MgO catalyst unlike palladium and platinum catalysts, which are prone to dehalogenation and poisoning of the metal by strong adsorption of the formed halogen . The slightly higher reaction time for conversion of ortho-substituted nitroarenes compared to the para-substituted ones indicated a steric effect.…”

Section: Resultsmentioning

confidence: 99%

Influencing the Electron Density of Nanosized Au Colloids via Immobilization on MgO to Stimulate Surface Reaction Activities

2020

View full text Add to dashboard Cite

Heterogenization of colloidal gold on MgO is demonstrated to facilitate its catalytic surface reactivity. We show that the electron density on Au influenced by its immobilization on MgO along with the ensued metal-support interaction is one of the key parameters to obtain high activity. As elucidated by X-ray absorption spectroscopic (X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, and extended X-ray absorption fine structure) studies, the presence of well-dispersed nanosized Au on MgO is observed to result in an enhancement in the electron density of Au. The consequence of this electron-rich gold on the catalytic activity is then investigated using the nitroarene reduction as a model reaction with a detailed kinetic study. The kinetic study is an attempt to use a true heterogeneous system rather than the usually studied quasi-homogeneous systems. The results obtained reveal that the Au/MgO catalyst has a surface rate constant of ∼1.39 × 10 −3 mol m −2 s −1 , which is significantly higher than those of the reported catalysts. While it validates the higher catalytic activity with a TOF of 9456 h −1 observed for Au/MgO, the increased adsorption constant for 4-nitrophenol on Au/MgO further reflects the efficacy of MgO as the support. This not only allows effective heterogenization of the Au nanoparticles keeping the catalyst stable under the reaction conditions and being reused several times but also renders a capability in reduction of other nitro group-containing substrates. Therefore, the results are believed to be of importance in designing heterogeneous catalysts utilizing the distinctive properties of the nanosized colloids and tuning their surface reactivity as well.

show abstract

“…Recently, a shape tunable iron pyrite (FeS 2 ) nanocrystal composed by iron oxy‐hydroxide (β ‐FeOOH) nanorods was successfully used for the selective reduction of functionalized nitroarenes to corresponding aniline [88a] . The β ‐FeOOH nanorods were obtained from the precipitation of aqueous FeCl 3 ⋅ 6H 2 O with polyethyleneimine (PEI, MW=750,000) at 80 °C for 2 h [88b] .…”

Section: Catalytic Transfer Hydrogenation Mediated By No‐palladium Trmentioning

confidence: 99%

Reduction of Nitroarenes via Catalytic Transfer Hydrogenation Using Formic Acid as Hydrogen Source: A Comprehensive Review

Romero

2020

ChemistrySelect

View full text Add to dashboard Cite

The reduction of nitroarenes to the corresponding aromatic amines is one of the most popular reactions in organic synthesis with significant application in pharmaceutical and manufacture industry. In the last decades, many efforts have been devoted to the design highly effective, chemoselective, low-cost and eco-friendly protocols. In this sense, the reduction of nitroarenes via transfer hydrogenation using formic acid as hydrogen source has gained great relevance with tremendous advance over the last year as an attractive and competitive strategy to classical protocols. The efforts have mainly been focused on the discovery of efficient catalyst based on advanced mesoporous support material loaded with transition metals or metallic nanoparticles, the optimization conditions for non-supported catalyst as well as convenient energy source to achieve an efficient and selective catalytic transfer hydrogenation (CTH) at room temperature. In the present review, several examples of reduction of nitroarenes using formic acid are shown as well as a comprehensive discussion about the role of catalyst, energy source and mechanism of reaction in the transfer hydrogenation process.

show abstract

Iron Pyrite Nanocrystals: A Potential Catalyst for Selective Transfer Hydrogenation of Functionalized Nitroarenes

Cited by 12 publications

References 75 publications

Synthesis of Magnetite Nanorods from the Reduction of Iron Oxy-Hydroxide with Hydrazine

Synthesis of Magnetite Nanorods from the Reduction of Iron Oxy-Hydroxide with Hydrazine

Influencing the Electron Density of Nanosized Au Colloids via Immobilization on MgO to Stimulate Surface Reaction Activities

Reduction of Nitroarenes via Catalytic Transfer Hydrogenation Using Formic Acid as Hydrogen Source: A Comprehensive Review

Contact Info

Product

Resources

About