Selective hydrogenation of benzonitrile in multiphase reaction systems including compressed carbon dioxide over Ni/Al2O3 catalyst

Cheng, Haiyang; Meng, Xiangchao; Wu, C. Y.; Shan, Xiaoyu; Yu, Yancun; Zhao, Fengyu

doi:10.1016/j.molcata.2013.07.017

Cited by 29 publications

(10 citation statements)

References 25 publications

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“…The transfer of PPA molecules into the aqueous phase may reduce the chance of PPA to react with intermediate species in the organic phase yielding the secondary amine. The formation of such carbamate species with CO2 was indicated for several amines in the literature [18,27,28]. The acidic nature of H2O would also have resulted in the higher conversion of PEC in n-hexane -CO2 -H2O than that in n-hexane -H2O.…”

Section: Resultsmentioning

confidence: 92%

Carbon dioxide and water: An effective multiphase medium for selective hydrogenation of nitriles with a Pd/Al2O3 catalyst

Bhosale

Yoshida

Fujita

et al. 2016

Journal of CO2 Utilization

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The effectiveness of a multiphase medium including CO2 and water was studied for the selective hydrogenation various nitriles of 2-phenylethyl cyanide (PEC), cinnamonitrile, nhexanenitrile (HN) and 4-cyanobiphenyl with a conventional Pd/Al2O3 catalyst. Such a multiphase reaction medium was observed to have different impacts changing from one nitrile to another and the selective production of primary amine was achieved with PEC and HN but not with the other nitriles. Possible reasons for the substrate-dependent effects of CO2 and water were discussed.

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Section: Resultsmentioning

confidence: 92%

Carbon dioxide and water: An effective multiphase medium for selective hydrogenation of nitriles with a Pd/Al2O3 catalyst

Bhosale

Yoshida

Fujita

et al. 2016

Journal of CO2 Utilization

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“…Among all 3d metals, Ni seems to be the most widely used metal for heterogeneous catalysis, such as methane reforming, [ 186‐187 ] partial oxidation of methane, [ 188 ] syngas methanation, [ 189‐190 ] hydrogenation of unsaturated chemicals [ 191‐192 ] and hydrogenolysis of hydrocarbons. Tracing back to the history of Ni catalysts, one pioneer study of investigaion of the particle size effect was about Ni‐catalyzed benzene hydrogenation and methane valorization reactions in 1980s, as seen in the review given by Che et al .…”

Section: Particle Size Effect In Metal Catalysismentioning

confidence: 99%

A Review on Particle Size Effect in Metal‐Catalyzed Heterogeneous Reactions

Wang

2020

Chin. J. Chem.

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Size of metal nanoparticles (NPs) plays decisive roles in metal-catalyzed heterogeneous reactions, due to the drastic variation of the geometric and electronic properties of metal NPs with size. Along with the development of controlled catalyst synthesis, tremendous efforts have been devoted to understanding the nature of the particle size effect. In particular, identification of the individual roles of size-dependent geometric and electronic effects on metal-catalyzed reactions is essential, but remains challenging since they are tightly hybridized together with particle size variation. In this review, we first discuss the fundamentals of the size-dependent geometric and electronic properties of metal NPs and their crucial roles in catalysis in general. Then we summarize the previous representative studies of the particle size effect, metal-by-metal, in heterogeneous catalysis. We highlighted the extension of particle size effect to ultrafine cluster and single-atom catalysts, the new frontiers in heterogeneous catalysis. In the followings, we further introduce the recent advances in disentangling the size-dependent geometric and electronic effects and unveiling their individual contributions to catalysis. Finally, we discuss the challenges and perspectives of investigations on the size effect in metal catalysis for the future studies. Mr. Hengwei Wang (left) received his B.Sc. degree from School of Chemistry and Materials Science, University of Science and Technology of China (USTC) in 2015. Then he Joined Professor Junling Lu's research group at USTC to pursue his doctorate in Physical Chemistry. His research focuses on atomically-precise design and synthesis of metal nanocatalysts for heterogeneous catalysis and unravelling their structure-reactivity relations at atomic scale. Prof. Junling Lu (right) received his Ph.D. degree from Institute of Physics, Chinese Academy of Sciences under the supervision of Prof. Hong-Jun Gao in 2007. During his Ph.D. studies, he visited Prof. Hans-Joachim Freund's group at Chemical Physics Department, Fritz-Haber-Institute, Max Planck Society as an exchange student in 2004-2006. After graduation, he spent three years in Prof. Peter C Stair's group at Northwestern University and then about two and a half years in Dr. Jeffrey W. Elam's group at Argonne National Laboratory as a Postdoc. In March 2013, he joined USTC as a Professor. His current research interest is atomically-precise design of a new generation of advanced catalysts through a combined wet-chemistry and atomic layer deposition (ALD) approach.

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“…Pt catalysts show a very different catalytic behavior, by producing DBA as the major product instead, and also along with a few percentage of TOL formation 16,21,22 . Transition metal Ni catalysts are also investigated, but show relatively lower hydrogenation activity even under much higher hydrogen pressures; therein, a mixture of BA, DBA, and the N-benzylidenebenzylamine (DBI) are generally observed 30,31 . The nature of metal catalysts appears to be the crucial factor that governs the reaction selectivity 4,28,32 .…”

Section: Introductionmentioning

confidence: 99%

Quasi Pd1Ni single-atom surface alloy catalyst enables hydrogenation of nitriles to secondary amines

et al. 2019

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Hydrogenation of nitriles represents as an atom-economic route to synthesize amines, crucial building blocks in fine chemicals. However, high redox potentials of nitriles render this approach to produce a mixture of amines, imines and low-value hydrogenolysis byproducts in general. Here we show that quasi atomic-dispersion of Pd within the outermost layer of Ni nanoparticles to form a Pd1Ni single-atom surface alloy structure maximizes the Pd utilization and breaks the strong metal-selectivity relations in benzonitrile hydrogenation, by prompting the yield of dibenzylamine drastically from ∼5 to 97% under mild conditions (80 °C; 0.6 MPa), and boosting an activity to about eight and four times higher than Pd and Pt standard catalysts, respectively. More importantly, the undesired carcinogenic toluene by-product is completely prohibited, rendering its practical applications, especially in pharmaceutical industry. Such strategy can be extended to a broad scope of nitriles with high yields of secondary amines under mild conditions.

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Selective hydrogenation of benzonitrile in multiphase reaction systems including compressed carbon dioxide over Ni/Al2O3 catalyst

Cited by 29 publications

References 25 publications

Carbon dioxide and water: An effective multiphase medium for selective hydrogenation of nitriles with a Pd/Al2O3 catalyst

Carbon dioxide and water: An effective multiphase medium for selective hydrogenation of nitriles with a Pd/Al2O3 catalyst

A Review on Particle Size Effect in Metal‐Catalyzed Heterogeneous Reactions

Quasi Pd1Ni single-atom surface alloy catalyst enables hydrogenation of nitriles to secondary amines

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