Room temperature selective reduction of nitrobenzene to azoxybenzene over magnetically separable urchin-like Ni/Graphene nanocomposites

Pahalagedara, Madhavi N.; Pahalagedara, Lakshitha; He, Jian; Miao, Ran; Gottlieb, Becca; Rathnayake, Dinithi; Suib, Steven L.

doi:10.1016/j.jcat.2016.01.007

Cited by 56 publications

(22 citation statements)

References 34 publications

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“…89,90,91,92,93 Azoxyarenes have been made through the selective reduction of nitroarenes or the selective oxidative of anilines. 94,95,96,97,98 Yet it is relatively uncommon for nitroarene reduction to stop at the azoxyarene intermediate step, making the Pd2Sn nanocrystals made here a much more interesting catalyst than we could have first envisioned, due to their catalytic activity and unique selectivity.…”

Section: Lpdpr 3 L + Pd + Prmentioning

confidence: 99%

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

et al. 2020

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Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Here, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10-14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials.

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Section: Lpdpr 3 L + Pd + Prmentioning

confidence: 99%

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

et al. 2020

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“…The electrochemical reduction of nitro substrate was first applied to the selective synthesis of azoxy-aromatic compounds, which is the most challenging synthetic task among azoxy-, azo- and amino-aromatics using reported methods [ 4 , 10–12 , 16 ]. The reaction was implemented in a 1.0 M KOH aqueous solution using a standard three-compartment electrochemical cell.…”

Section: Selective Electrochemical Reduction Of Nitroarenes To Azoxy- Azo- and Amino-aromaticsmentioning

confidence: 99%

Potential-tuned selective electrosynthesis of azoxy-, azo- and amino-aromatics over a CoP nanosheet cathode

Chong

Liu

Huang

et al. 2019

National Science Review

123

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Azoxy-, azo- and amino-aromatics are among the most widely used building blocks in materials science pharmaceuticals and synthetic chemistry, but their controllable and green synthesis has not yet been well established. Herein, a facile potential-tuned electrosynthesis of azoxy-, azo- and amino-aromatics via aqueous selective reduction of nitroarene feedstocks over a CoP nanosheet cathode is developed. A series of azoxy-, azo- and amino-compounds with excellent selectivity, good functional group tolerance and high yields are produced by applying different bias input. The synthetically significant and challenging asymmetric azoxy-aromatics can be controllably synthesized in moderate to good yields. The use of water as the hydrogen source makes this strategy remarkably fascinating and promising. In addition, deuterated aromatic amines with a high deuterium content can be readily obtained by using D2O. By pairing with anodic oxidation of aliphatic amines to nitriles, synthetically useful building blocks can be simultaneously produced in a CoP||Ni2P two-electrode electrolyzer. Only 1.25 V is required to achieve a current density of 20 mA cm−2, which is much lower than that of overall water splitting (1.70 V). The paired oxidation and reduction reactions can also be driven using a 1.5 V battery to synthesize nitrile and azoxybenzene with good yields and selectivity, further emphasizing the flexibility and controllability of our method. This work paves the way for a promising approach to the green synthesis of valuable chemicals through potential-controlled electrosynthesis.

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“…Catalytic transfer hydrogenation opens up a new dimension in reduction of organic compounds because of operational safety and enhanced degree of control in selectivity compared with the conventional molecular hydrogen-based process. Non-NM catalysts as an alternative for precious metals have attracted extensive attention due to their low cost and abundance but suffering from their relatively poor catalytic activity and selectivity (34). In this context, we fabricate an inverse structure with Ni particles surrounded by CeO 2 nanoparticles (denoted as Ni@CeO 2 -IE; see Fig.…”

Section: Ni@ceo 2 -Ie Surrounded Catalysts With Inverse Structure (Fomentioning

confidence: 99%

Surrounded catalysts prepared by ion-exchange inverse loading

et al. 2020

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The supported catalyst featuring highly dispersed active phase on support is the most important kind of industrial catalyst. Extensive research has demonstrated the critical role (in catalysis) of the interfacial interaction/perimeter sites between the active phase and support. However, the supported catalyst prepared by traditional methods generally presents low interface density because of limit contact area. Here, an ion-exchange inverse loading (IEIL) method has been developed, in which the precursor of support is controllably deposited onto the precursor of active phase by ion-exchange reaction, leading to an active core surrounded (by support) catalyst with various structures. The unique surrounded structure presents not only high interface density and mutually changed interface but also high stability due to the physical isolation of active phase, revealing superior catalytic performances to the traditional supported catalysts, suggesting the great potential of this new surrounded catalyst as the upgrade of supported catalyst in heterogeneous catalysis.

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Room temperature selective reduction of nitrobenzene to azoxybenzene over magnetically separable urchin-like Ni/Graphene nanocomposites

Cited by 56 publications

References 34 publications

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Potential-tuned selective electrosynthesis of azoxy-, azo- and amino-aromatics over a CoP nanosheet cathode

Surrounded catalysts prepared by ion-exchange inverse loading

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