High performance of a cobalt–nitrogen complex for the reduction and reductive coupling of nitro compounds into amines and their derivatives

Zhou, Peng; Jiang, Liang; Wu, Fan; Lv, Kangle; Zhang, Zehui

doi:10.1126/sciadv.1601945

Cited by 227 publications

(163 citation statements)

References 51 publications

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“…This system also allows the selective production (93–98 %) of substituted anilines from functionalized nitroarenes. High performances of Co SAC on N‐doped carbon supports were also reported by Zhang et al . The Co 1 /N−C SAC showed good performances in terms of activity, selectivity, and stability for the reduction under dihydrogen (3.5 bar) at 110 °C of various nitro compounds.…”

Section: Catalysis With Single Atom Catalysts On Carbon‐based Materialssupporting

confidence: 69%

Single Atom Catalysts on Carbon‐Based Materials

2018

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Metal particle size is an important parameter to consider when looking at supported catalyst performances. As for other properties, surface reactivity of metallic nanoparticles is thus highly size‐dependent. The smallest size that can be reached for this type of object is of course the isolated atom deposited on a support. The preparation of single‐atom catalysts (SAC) is not trivial, since to avoid clustering, the mean adsorption energy of the metal on the support should be higher than its cohesive energy. The choice of a support that allows a strongly interacting environment with the metal is therefore a key step in the preparation of such catalysts. The spectrum of carbon (nano)materials is very broad, and their structure as well as their surface chemistry, although sometime complex, can be tuned and exploited for the stabilization of SAC. This Review summarizes in a comprehensive manner experimental and computational studies aiming at: i) preparing SAC on carbon materials, ii) understanding the metal‐support interactions in SAC, and iii) studying how this relates to catalytic performances. The use of SAC follows well the needs dictated by society (energy and environment issues), and many studies have already been published in various fields, such as thermal catalysis, photocatalysis and electrocatalysis.

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Section: Catalysis With Single Atom Catalysts On Carbon‐based Materialssupporting

confidence: 69%

Single Atom Catalysts on Carbon‐Based Materials

2018

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“…Furthermore, azo compound by‐products produced from the catalytic reduction of 2,4‐dinitroaniline were not further converted to 2,4‐diaminoaniline using excess reductants. Hence, the hydrogenation of nitrobenzene with N 2 H 4 ⋅H 2 O over Co@ZDC@mC nanoreactor catalysts follows the mechanism of the “direct pathway” rather than the “condensation way.” Scheme shows the speculative specific reaction process . First, N 2 H 4 ⋅H 2 O entered the nanoreactor and diffused to the Co NP surface, followed by the bond dissociation to form nitrogen and surface‐bound hydrogen as metal hydrides.…”

Section: Resultsmentioning

confidence: 99%

Co‐MOF‐Derived Hierarchical Mesoporous Yolk‐shell‐structured Nanoreactor for the Catalytic Reduction of Nitroarenes with Hydrazine Hydrate

et al. 2019

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Porous nanoreactors demonstrate immense potential for applications in heterogeneous catalysis due to their excellent mass‐transfer performance and stability. The design of a simple, universal strategy for fabricating nanoreactor catalysts is of significance for organic transformation. In this study, a nanoreactor with a hierarchical mesoporous yolk‐shell structure was successfully prepared by the high‐temperature carbonization of a ZIF‐67@polymer composite. The core of the resultant Co@ZDC@mC material comprised Co NPs anchored in the ZIF‐67‐derived carbon framework, while the shell comprised resin‐polymer‐derived mesoporous carbon. The as‐obtained Co@ZDC@mC‐700 catalyst enriched reactants, efficiently catalyzed the reaction in the core, and permitted the desorption of the product from the nanoreactor. In the catalytic reduction of nitrobenzene with N2H4⋅H2O, Co@ZDC@mC‐700 exhibited superior catalytic efficiency (TOF=1136.3 h−1). In addition, Co@ZDC@mC‐700 exhibited excellent performance for the catalytic reduction of various functionalized nitroarenes, as well as good reusability and recyclability. Hence, a simple, useful approach for fabricating a metal‐organic‐framework‐derived non‐noble metal‐based yolk‐shell nanoreactor for effective catalytic transformation is proposed.

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“…Powder X‐ray diffraction (XRD) was carried out to confirm that the PRO effectively controlled the Rh NPs formation in small sizes and immobilized by carbon (Figure S5). All the XRD patterns of the samples showed two broad peaks located at 2 θ =25° and 43°, which are almost consistent with the peak shape of the carbon support . No visible diffraction peaks of Rh were observed, which could be attributed to the ultrasmall size of Rh NPs and the low loading of Rh in PRO‐Rh/C.…”

Section: Resultsmentioning

confidence: 99%

Ultrahigh Catalytic Activity of l‐Proline‐Functionalized Rh Nanoparticles for Methanolysis of Ammonia Borane

Luo

Cheng

et al. 2018

ChemSusChem

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The synthesis of ultrafine and well‐distributed rhodium nanoparticles (NPs) with high efficiency toward methanolysis of ammonia borane (AB) is crucially important but challenging. A facile approach has been developed for synthesizing ultrafine and uniform Rh NPs deposited on carbon by using the small soluble organic molecule (SOM) of l‐proline (PRO) as capping agent (Rh‐PRO/C). The enrichment of N,O‐coordination sites for the metal precursor by using PRO was found to be the key to the synthesis Rh‐PRO/C. The as‐prepared Rh‐PRO/C showed high catalytic activity for ammonia borane methanolysis with the highest total turnover frequency (TOF) of 1035 molnormalH2 (molRh min)−1 under basic conditions, which was three times higher than that of the state‐of‐the‐art Rh‐based catalysts. The excellent catalytic performance of Rh‐PRO/C was ascribed to the well‐dispersed Rh NPs and the PRO‐functionalized metal surface, which can provide more active sites for the reaction. The merit of size‐controlled synthesis combined with metal NP surface modification by SOMs is likely to be beneficial in various catalytic fields.

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High performance of a cobalt–nitrogen complex for the reduction and reductive coupling of nitro compounds into amines and their derivatives

Abstract: The cobalt–nitrogen catalyst shows high activity for selective reduction of nitro compounds with H2 and other hydrogen donors.

Cited by 227 publications

References 51 publications

Single Atom Catalysts on Carbon‐Based Materials

Single Atom Catalysts on Carbon‐Based Materials

Co‐MOF‐Derived Hierarchical Mesoporous Yolk‐shell‐structured Nanoreactor for the Catalytic Reduction of Nitroarenes with Hydrazine Hydrate

Ultrahigh Catalytic Activity of l‐Proline‐Functionalized Rh Nanoparticles for Methanolysis of Ammonia Borane

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