One-step synthesis of nitriles by the dehydrogenation–amination of fatty primary alcohols over Cu/m-ZrO2

Hu, Yinchang; Jin, Shuhan; Zhang, Zhichao; Zhang, Likun; Deng, Jun; Zhang, Hongsheng

doi:10.1016/j.catcom.2014.05.010

Cited by 20 publications

(10 citation statements)

References 21 publications

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“…Cu-based catalysts have been reported to be potential catalysts for the production of amines via the amination of alcohols due to the excellent selectivity toward hydrogenation/dehydrogenation for CN/ CH-OH bonds rather than CC/C-C bonds. 31,32 Thus, many efforts have been made towards alcohol amination over Cubased catalysts. 30,[33][34][35] Nevertheless, The investigation of BDMAEE from DEG and DMA via a heterogeneous process is seldom reported.…”

Section: Introductionmentioning

confidence: 99%

Cr and Co-modified Cu/Al₂O₃ as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether

Zeng

Wang

et al. 2022

Catal. Sci. Technol.

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Section: Introductionmentioning

confidence: 99%

Cr and Co-modified Cu/Al₂O₃ as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether

Zeng

Wang

et al. 2022

Catal. Sci. Technol.

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“…Despite the commercial significance of nitriles, their traditional preparation methods, including Sandmeyer reaction, Rosenmund–von Braun reaction, and nucleophilic substitution of cyanides to alkyl and aryl halides, generally require toxic starting materials and harsh reaction conditions. − In addition, stoichiometric amounts of chemical wastes are often produced. Primary alcohols represent a class of alternative, greener starting material, , which can be converted to nitriles through oxygen-involved ammoxidation − or amination–dehydrogenation − reactions generating only H 2 O and H 2 as byproducts. Limited selectivity due to overoxidation and/or high energy consumption associated with high reaction temperatures (280–500 °C) are the significant disadvantages in the current transformation of alcohols to nitriles using heterogeneous catalysts.…”

Section: Introductionmentioning

confidence: 99%

Identification of an Active NiCu Catalyst for Nitrile Synthesis from Alcohol

2019

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Development of heterogeneous catalysts for alcohol transformation into nitriles under oxidant-free conditions is a challenge. Considering the C–H activation on α-carbon of primary alcohols is the rate-determining step, decreasing the activation energy of C–H activation is critical in order to enhance the catalytic activity. Several NiM/Al2O3 bimetallic catalysts were synthesized and scrutinized in catalytic transformation of 1-butanol to butyronitrile. Ni–Cu was identified as a suitable combination with the optimized Ni0.5Cu0.5/Al2O3 catalyst exhibiting 10 times higher turnover frequency than Ni/Al2O3 catalyst. X-ray absorption spectroscopy (XAS) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) revealed that the NiCu particles in the catalyst exist in the form of homogeneous alloys with an average size of 8.3 nm, providing an experimental foundation to build up a catalyst model for further density functional theory (DFT) calculations. Calculations were done over a series of NiM catalysts, and the experimentally observed activity trend could be rationalized by the Brønsted–Evans–Polanyi (BEP) principle, i.e., catalysts that afford reduced reaction energy also feature lower activation barriers. The calculated activation energy (E a) for C–H activation with coadsorbed NH3 dropped from 63.4 kJ/mol on pure Ni catalyst to 49.9 kJ/mol on the most active NiCu-2 site in NiCu bimetallic catalyst, in good agreement with the experimentally measured activation energy values. The Ni0.5Cu0.5/Al2O3 catalyst was further employed to convert 11 primary alcohols into nitriles with high to near-quantitative yields, at a Ni loading 10 times less than that of the conventional Ni/Al2O3 catalyst.

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“…103 The exceptionally high activation energy of C−H bond activation on Cu surface implies high temperature is necessary for Cu catalyst to be effective. Indeed, close to 300 °C is required for alcohol conversion into nitriles over Cu NPs, 146,147 in sharp contrast with Ni catalyst that exhibited activity at 190 °C. 148 For carbonyl group transformation where no C−H bond cleavage is needed, Cu catalyst exhibited satisfactory performance at much lower temperature (80 °C).…”

Section: Understanding the Metal-dependent Activitymentioning

confidence: 99%

“…While these catalysts were active in transforming one specific substrate, their wide application in more substrates was not verified. Hu et al introduced a Cu/m-ZrO 2 catalyst which effectively converts C 3 –C 8 primary alcohols to nitriles in ammonia flow at 280 °C …”

Section: Production Of Organonitrogen Chemicals From Oxygen-containin...mentioning

confidence: 99%

“…Hu et al introduced a Cu/m-ZrO 2 catalyst which effectively converts C 3 −C 8 primary alcohols to nitriles in ammonia flow at 280 °C. 147 In these earlier reports, the catalysts required high temperature to operate (280−500 °C). As a result, catalyst deactivation, product decomposition, and intense energy consumption are associated with these processes, placing challenges for scaling up applications.…”

Section: Acs Catalysismentioning

confidence: 99%

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Organonitrogen Chemicals from Oxygen-Containing Feedstock over Heterogeneous Catalysts

et al. 2019

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Organonitrogen chemicals, such as amines, nitriles, amides, amino acids, and N-heterocycles, are ubiquitous building blocks in chemical industry. Conventional methodologies to prepare these chemicals, however, suffer from using toxic, corrosive starting materials and/or employing harsh reaction conditions. Recent advances suggest that heterogeneous catalysts are promising to promote the formation of organonitrogen chemicals from cheap and abundant materials. In this Review, we summarize the most recent developments using supported solid catalysts to make organonitrogen chemicals from oxygen-containing feedstock and NH3. We introduce four key transformations including carbonyls/alcohols to amines, alcohols/carbonyls to nitriles, alcohols/nitriles to amides, and alcohols/carbonyls to N-heterocycles. In each section, the function of the catalyst and the structure–activity correlations are discussed. Auxiliary factors affecting the performance of the catalysts, such as solvent effect, substituent group effect, and/or reactor design are also reviewed.

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One-step synthesis of nitriles by the dehydrogenation–amination of fatty primary alcohols over Cu/m-ZrO2

Cited by 20 publications

References 21 publications

Cr and Co-modified Cu/Al₂O₃ as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether

Cr and Co-modified Cu/Al₂O₃ as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether

Identification of an Active NiCu Catalyst for Nitrile Synthesis from Alcohol

Organonitrogen Chemicals from Oxygen-Containing Feedstock over Heterogeneous Catalysts

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One-step synthesis of nitriles by the dehydrogenation–amination of fatty primary alcohols over Cu/m-ZrO2

Cited by 20 publications

References 21 publications

Cr and Co-modified Cu/Al2O3 as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether

Cr and Co-modified Cu/Al2O3 as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether

Identification of an Active NiCu Catalyst for Nitrile Synthesis from Alcohol

Organonitrogen Chemicals from Oxygen-Containing Feedstock over Heterogeneous Catalysts

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Product

Resources

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Cr and Co-modified Cu/Al₂O₃ as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether

Cr and Co-modified Cu/Al₂O₃ as an efficient catalyst for the continuous synthesis of bis(2-dimethylaminoethyl)ether