Turning the product selectivity of nitrile hydrogenation from primary to secondary amines by precise modification of Pd/SiC catalysts using NiO nanodots

Jiao, Zhifeng; Zhao, Ji-Xiao; Guo, Xiaoning; Tong, Xili; Zhang, Bin; Jin, Guojun; Qin, Yong; Guo, Xiang‐Yun

doi:10.1039/c9cy00353c

Cited by 30 publications

(16 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, the low H 2 O 2 turnover rate in some aprotic solvents might be assigned to the poisoning effect of the solvents. In addition, it has been found that some solvents, such as ACN, can be reduced by H 2 in moderate temperature on Pd catalyst, 58 which might be another possible reason to explain the low H 2 O 2 turnover rate in some aprotic solvents.…”

Section: Methodsmentioning

confidence: 99%

Facet-Dependent of Catalytic Selectivity: The Case of H₂O₂ Direct Synthesis on Pd Surfaces

et al. 2019

View full text Add to dashboard Cite

Pd catalysts display excellent potential applications in H 2 O 2 direct synthesis from H 2 and O 2 . Facet dependence on catalytic selectivity for H 2 O 2 direct synthesis on Pd surfaces is investigated by the combination of DFT calculations and microkinetic study. It is found that the coadsorbed O plays a key role in catalytic activity and selectivity for H 2 O 2 direct synthesis on Pd(111) and Pd(100) surfaces. The coadsorbed O on Pd surfaces could not only increase the catalytic activity but also promote the catalytic selectivity on Pd surfaces. With the help of coadsorbed O, Pd(111) surface shows a very high selectivity (>99%) for H 2 O 2 products, but Pd(100) surface displays a high selectivity (>99%) for H 2 O formation. The role of proton transfer is also investigated in H 2 O 2 direct synthesis, and it is found that proton transfer reactions are harmful to H 2 O 2 formation. This work sheds light on the reaction mechanism of H 2 O 2 direct synthesis reaction on different Pd surfaces, and it may create a new path to understand the facet-dependent on catalytic selectivity.

show abstract

Section: Methodsmentioning

confidence: 99%

Facet-Dependent of Catalytic Selectivity: The Case of H₂O₂ Direct Synthesis on Pd Surfaces

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Thus, the selectivity of products is intensively determined by the lifetime of the intermediate imine. By extending the lifetime of the intermediate imines, it is prior to obtain secondary amines . Thus, we modified the Pt−Cu catalyst with a fourth component to weaken the effect of copper so as to improve the selectivity of secondary amines.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, there are some inspiring results about the hydrogenation of nitriles to secondary amine with H 2 as hydrogen source . Jiao's group reported a 5NiO−Pd/SiC catalyst for the hydrogenation of nitriles with H 2 to secondary amines by the modification of NiO nanodots . Direct hydrogenation usually requires pressurized hydrogen or ultralong reaction time, which produce the hydrogenolysis by‐products .…”

Section: Introductionmentioning

confidence: 99%

Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt−CuFe/Fe₃O₄ Catalyst and Ammonia Borane as Hydrogen Donor

Guo

Liu

et al. 2020

ChemPlusChem

View full text Add to dashboard Cite

Hydrogenation of nitriles is an efficient and environmentally friendly route to synthesize symmetrical secondary amines, but it usually produces a mixture of amines, imines, and hydrogenolysis by‐products. Herein we report a magnetic quaternary‐component Pt−CuFe/Fe3O4 nanocatalyst system for the selective synthesis of symmetrical secondary amines with ammonia borane as hydrogen donor. The catalyst with a low Pt loading (0.456 wt%) is the source of the activity, and the d‐band electron transfer from Cu to Fe enhances the selectivity. This synergistic effect results in the transformation of benzonitrile to dibenzylamine with excellent conversion (up to 99 %) and nearly quantitative selectivity (up to 96 %) under mild reaction conditions, nevertheless, the reaction TOF is as high as up to 1409.9 h−1. A variety of nitriles are suitable for the synthesis of symmetrical secondary amines. More importantly, unwanted hydrogenolysis byproducts, especially toluene, is not detected at all. In addition, the catalyst is magnetically recoverable, and it can be reused up to five times.

show abstract

“…[63] As a promising crystalline porous material, metal-organic frameworks (MOFs) are often employed as precursors to prepare transition alloy nanoparticles, which show high catalytic activity for the hydrogenation of nitriles. [12,13,64] Ni, Co and Ru supported on SiO 2 , [61] Pd supported on SiC, [65] Fe 3 O 4 [66] and other catalyst supports are also widely used in nitrile hydrogenation. In 2016, Li et al [64a] designed a bifunctional N-doped Co@C catalyst, Co@NC-900 73, which was prepared from pyrolyzing the N-containing CoÀ MOF at 900 °C.…”

Section: The Hydrogenation Reaction Of Nitriles In Heterogeneous Systemmentioning

confidence: 99%

Recent Advances in Chemical Modifications of Nitriles

Xia

Jiang

2021

Eur J Org Chem

View full text Add to dashboard Cite

Nitrile represents a synthetically important class of compounds, relevant to the preparation of fine organic chemicals, natural products, and biologically active molecules. The electronegative nitrogen atom and electropositive carbon atom of cyano group endow nitriles with rich and diverse chemical properties. Traditional chemical transformations of nitriles usually involve the use of strong acids, bases, and other harsh conditions. To overcome these limitations, various catalytic methods have been explored both in homogeneous and heterogeneous systems. In this review, we summarize some of the recent progress on the development of efficient synthetic methods involving nitriles. Especially, the classic transformations of nitriles including hydration, hydrolysis and reduction reactions are discussed in detail, which provide rapid access to a series of important small molecules, such as amides, ketones, amines, and imines. The reaction development, as well as the design of the catalytic system will be discussed with special emphasis placed on the mechanistic aspects.

show abstract

Turning the product selectivity of nitrile hydrogenation from primary to secondary amines by precise modification of Pd/SiC catalysts using NiO nanodots

Abstract: The selectivity of nitrile hydrogenation was turned by the concentration of hydrogen radicals on Pd surface.

Cited by 30 publications

References 49 publications

Facet-Dependent of Catalytic Selectivity: The Case of H₂O₂ Direct Synthesis on Pd Surfaces

Facet-Dependent of Catalytic Selectivity: The Case of H₂O₂ Direct Synthesis on Pd Surfaces

Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt−CuFe/Fe₃O₄ Catalyst and Ammonia Borane as Hydrogen Donor

Recent Advances in Chemical Modifications of Nitriles

Contact Info

Product

Resources

About

Turning the product selectivity of nitrile hydrogenation from primary to secondary amines by precise modification of Pd/SiC catalysts using NiO nanodots

Abstract: The selectivity of nitrile hydrogenation was turned by the concentration of hydrogen radicals on Pd surface.

Cited by 30 publications

References 49 publications

Facet-Dependent of Catalytic Selectivity: The Case of H2O2 Direct Synthesis on Pd Surfaces

Facet-Dependent of Catalytic Selectivity: The Case of H2O2 Direct Synthesis on Pd Surfaces

Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt−CuFe/Fe3O4 Catalyst and Ammonia Borane as Hydrogen Donor

Recent Advances in Chemical Modifications of Nitriles

Contact Info

Product

Resources

About

Facet-Dependent of Catalytic Selectivity: The Case of H₂O₂ Direct Synthesis on Pd Surfaces

Facet-Dependent of Catalytic Selectivity: The Case of H₂O₂ Direct Synthesis on Pd Surfaces

Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt−CuFe/Fe₃O₄ Catalyst and Ammonia Borane as Hydrogen Donor