Graphene hydrogel supported palladium nanoparticles as an efficient and reusable heterogeneous catalysts in the transfer hydrogenation of nitroarenes using ammonia borane as a hydrogen source

2018 ◽  
Vol 90 (2) ◽  
pp. 327-335 ◽  
Author(s):  
Paria Eghbali ◽  
Bilal Nişancı ◽  
Önder Metin

Abstract Addressed herein is a facile one-pot synthesis of graphene hydrogel (GHJ) supported Pd nanoparticles (NPs), namely Pd-GHJ nanocomposites, via a novel method that comprises the combination of hydrothermal treatment and polyol reduction protocols in water. The structure Pd-GHJ nanocomposites were characterized by TEM, HR-TEM, XRD, XPS, Raman spectroscopy and BET surface area analysis. Then, Pd-GHJ nanocomposites were used as a heterogeneous catalysts in the tandem dehydrogenation of ammonia borane and hydrogenation of nitroarenes (Ar–NO2) to anilines (Ar–NH2) in the water/methanol mixture at room temperature. A variety of Ar–NO2 derivatives (total 9 examples) were successfully converted to the corresponding Ar–NH2 by the help of Pd-GHJ nanocomposites catalyzed tandem reactions with the conversion yields reaching up to 99% in only 20 min reaction time. Moreover, Pd-GHJ nanocomposites were demonstrated to be the reusable catalysts in the tandem reactions by preserving their initial catalytic performance after five consecutive catalytic cycles. It is believed that the presented synthesis protocol for the Pd-GHJ nanocomposites and the catalytic tandem hydrogenation reactions will make a significant contribution to the catalysis and synthetic organic chemistry fields.

2019 ◽  
Vol 44 (1-2) ◽  
pp. 14-19
Author(s):  
Bilal Nişancı ◽  
Ziya Dağalan

A novel transfer hydrogenation methodology for the reduction of ketones (14 examples) and benzaldehyde derivatives (12 examples) to the corresponding alcohols using Pd nanoparticles supported on mesoporous graphitic carbon nitride (mpg-C3N4/Pd) as a reusable catalyst and ammonia borane as a safe hydrogen source in an aqueous solution MeOH/H2O (v/v = 1/1) is described. The catalytic hydrogenation reactions were conducted in a commercially available high-pressure glass tube at room temperature, and the corresponding alcohols were obtained in high yields in 2–5 min. Moreover, the presented transfer hydrogenation protocol shows partial halogen selectivity with bromo-, fluoro-, and chloro-substituted carbonyl analogs. In addition, the present catalyst can be reused up to five times without losing its efficiency, and scaling-up the reaction enables α-methylbenzyl alcohol to be produced in 90% isolated yield.


2016 ◽  
Vol 4 (26) ◽  
pp. 10254-10262 ◽  
Author(s):  
Jilan Long ◽  
Kui Shen ◽  
Liang Chen ◽  
Yingwei Li

We report a MOF-templated route to synthesize transition metal alloy NPs embedded in an N-doped carbon matrix. The alloy-based catalysts exhibited excellent catalytic performance and widespread substrate applicability for the transfer hydrogenation of nitriles.


2017 ◽  
Vol 19 (16) ◽  
pp. 3759-3763 ◽  
Author(s):  
Priscilla N. Paulino ◽  
Rafael F. Perez ◽  
Natália G. Figueiredo ◽  
Marco A. Fraga

Dehydration and transfer hydrogenation tandem reactions of xylose to furfuryl alcohol in water/isopropanol were performed on MFI, FAU and BEA zeolites.


2021 ◽  
Vol 9 ◽  
Author(s):  
Yixuan Liu ◽  
Xixi Liu ◽  
Mingrui Li ◽  
Ye Meng ◽  
Jie Li ◽  
...  

The massive burning of a large amount of fossil energy has caused a lot of serious environmental issues (e.g., air pollution and climate change), urging people to efficiently explore and valorize sustainable alternatives. Biomass is being deemed as the only organic carbon-containing renewable resource for the production of net-zero carbon emission fuels and fine chemicals. Regarding this, the selective transformation of high-oxygen biomass feedstocks by catalytic transfer hydrogenation (CTH) is a very promising strategy to realize the carbon cycle. Among them, the important Meerwein-Ponndorf-Verley (MPV) reaction is believed to be capable of replacing the traditional hydrogenation strategy which generally requires high-pressure H2 and precious metals, aiming to upgrade biomass into downstream biochemical products and fuels. Employing bifunctional heterogeneous catalysts with both acidic and basic sites is needed to catalyze the MPV reaction, which is the key point for domino/cascade reaction in one pot that can eliminate the relevant complicated separation/purification step. Zirconium (Zr) and hafnium (Hf), belonging to transition metals, rich in reserves, can demonstrate similar catalytic efficiency for MPV reaction as that of precious metals. This review introduced the application of recyclable heterogeneous non-noble Zr/Hf-containing catalysts with acid-base bifunctionality for CTH reaction using the safe liquid hydrogen donor. The corresponding catalysts were classified into different types including Zr/Hf-containing metal oxides, supported materials, zeolites, metal-organic frameworks, metal-organic hybrids, and their respective pros and cons were compared and discussed comprehensively. Emphasis was placed on evaluating the bifunctionality of catalytic material and the key role of the active site corresponding to the structure of the catalyst in the MPV reaction. Finally, a concise summary and prospect were also provided centering on the development and suggestion of Zr/Hf-containing acid-base bifunctional catalysts for CTH.


2020 ◽  
Vol 16 ◽  
pp. 2477-2483 ◽  
Author(s):  
Tony Jin ◽  
Malickah Hicks ◽  
Davis Kurdyla ◽  
Sabahudin Hrapovic ◽  
Edmond Lam ◽  
...  

In this report, chitin and chitosan nanocrystals were used as biomass-based supports for Pd nanoparticles (NPs) used as a heterogeneous catalyst for the Heck coupling reaction. By using a one-pot fabrication method, a Pd salt precursor was directly reduced and deposited onto these nanocrystal catalysts. Characterization of these nanocomposites showed disperse Pd NPs on the surfaces of the chitinous nanocrystals. Heck coupling model reactions revealed full product yield in relatively benign conditions, outcompeting the use of other catalysts supported on biomass-based nanomaterials, including cellulose nanocrystals. These initial results show the potential for using chitinous nanomaterials as effective catalyst supports in cross-coupling reactions.


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