Density functional theory study of <i>p</i>‐chloroaniline adsorption on Pd surfaces and clusters

He, Xiaobo; Lyu, Jinghui; Zhou, Hu; Zhuang, Guilin; Zhong, Xing; Wang, Jianguo; Li, Xiaonian

doi:10.1002/qua.24681

Cited by 6 publications

(7 citation statements)

References 43 publications

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“…Core electron interactions were described with the projector- augmented wave (PAW) method 40 . The methods used have been applied to DFT studies of arene derivatives and surface sites of Pd nanoparticles 41 .…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of ketones from biomass-derived feedstock

et al. 2017

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Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in H2O/CH2Cl2 can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory. Detailed study shows that the Pd, bromide salt and H2O/CH2Cl2 work cooperatively to promote the desired reaction and inhibit the side reaction. Thus high yields of desired products can be obtained. This work opens the way for production of ketones from aromatic ethers that can be derived from biomass.

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Section: Methodsmentioning

confidence: 99%

“…where E ads , E molecule+slab , E molecule and E slab represents the adsorption energy, the total energy after molecule is adsorbed on the slab Pd (111) surface, the energy of isolated molecule, and the total energy of the slab, respectively 41 .…”

Section: Methodsmentioning

confidence: 99%

Synthesis of ketones from biomass-derived feedstock

et al. 2017

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“…40,41 Therefore, the Pd(211) surface is modeled using a p(1 × 3) surface unit cell 42 with four layers in the z-direction, and a vacuum thickness of 12 Å is employed to avoid interactions between slabs. It is a common method to deal with the interaction and reactions between gases and solid modeling by the slab, which is widely used in the different gases adsorption and reactions on the Pd(211) surface, 43,44 as well as the activation of NO and reduction by H 2 . 45,24 The bottom two layers are kept frozen to their optimized bulk positions, while the others were allowed to relax.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The stepped Pd(211) surface has been investigated by XRD spectra when Pd was loaded on C, SnO 2 /C and SnO 2 /multiwalled carbon nanotubes (MWCNTs), , which was also built as a catalytic surface to study the adsorption and reaction of gases in theory. , Therefore, the Pd(211) surface is modeled using a p (1 × 3) surface unit cell with four layers in the z -direction, and a vacuum thickness of 12 Å is employed to avoid interactions between slabs. It is a common method to deal with the interaction and reactions between gases and solid modeling by the slab, which is widely used in the different gases adsorption and reactions on the Pd(211) surface, , as well as the activation of NO and reduction by H 2 . , The bottom two layers are kept frozen to their optimized bulk positions, while the others were allowed to relax. The isolated molecules and atoms are optimized in a large cell of 10 × 10 × 10 Å.…”

Section: Computational Detailsmentioning

confidence: 99%

Insight into the Reduction of NO by H₂ on the Stepped Pd(211) Surface

et al. 2017

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A periodic density functional theory (DFT) calculation has been used to study the NO reduction by H 2 on the stepped Pd(211) surface. The main route of N 2 generation changes with temperature increasing. The dimer path is main for the formation of N 2 at low temperature, in which two NO react and generate N 2 O 2 , and then N 2 O 2 decompose to produce N 2 . However, the active N path becomes main to generate N 2 via NO hydrogenate and dissociate to produce active N at high temperature. The formation of NH 3 is via the successive hydrogenation of N or NH. Additionally, energy barriers showed that the Pd(211) surface exhibited higher catalytic activity to the reduction of NO by H 2 than that on the Pd(111) surface, and the kinetics showed that the selectivity of N 2 is higher than that of NH 3 on the stepped Pd(211) surface below about 500 K.

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“…In a comparison with other systems, DFT calculations were utilized to estimate the adsorption energies of p -CAN over several Pd surfaces (including steeped, flat) and clusters. Adsorption energies were found to reside in the range of −39.2 to −61.11 kcal/mol …”

Section: Resultsmentioning

confidence: 99%

Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo₂N

et al. 2018

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Promoting the production of industrially important aromatic chloroamines over transition-metal nitrides catalysts has emerged as a prominent theme in catalysis. This contribution provides an insight into the reduction mechanism of p -chloronitrobenzene ( p -CNB) to p -chloroaniline ( p -CAN) over the γ-Mo 2 N(111) surface by means of density functional theory calculations. The adsorption energies of various molecularly adsorbed modes of p -CNB were computed. Our findings display that, p -CNB prefers to be adsorbed over two distinct adsorption sites, namely, Mo-hollow face-centered cubic (fcc) and N-hollow hexagonal close-packed (hcp) sites with adsorption energies of −32.1 and −38.5 kcal/mol, respectively. We establish that the activation of nitro group proceeds through direct pathway along with formation of several reaction intermediates. Most of these intermediaries reside in a significant well-depth in reference to the entrance channel. Central to the constructed mechanism is H-transfer steps from fcc and hcp hollow sites to the NO/–NH groups through modest reaction barriers. Our computed rate constant for the conversion of p -CNB correlates very well with the experimental finding (0.018 versus 0.033 s –1 at ∼500 K). Plotted species profiles via a simplified kinetics model confirms the experimentally reported high selectivity toward the formation of p -CAN at relatively low temperatures. It is hoped that thermokinetics parameters and mechanistic pathways provided herein will afford a molecular level understanding for γ-Mo 2 N-mediated conversion of halogenated nitrobenzenes into their corresponding nitroanilines; a process that entails significant industrial applications.

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Density functional theory study of p‐chloroaniline adsorption on Pd surfaces and clusters

Cited by 6 publications

References 43 publications

Synthesis of ketones from biomass-derived feedstock

Synthesis of ketones from biomass-derived feedstock

Insight into the Reduction of NO by H₂ on the Stepped Pd(211) Surface

Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo₂N

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Density functional theory study of p‐chloroaniline adsorption on Pd surfaces and clusters

Cited by 6 publications

References 43 publications

Synthesis of ketones from biomass-derived feedstock

Synthesis of ketones from biomass-derived feedstock

Insight into the Reduction of NO by H2 on the Stepped Pd(211) Surface

Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo2N

Contact Info

Product

Resources

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Insight into the Reduction of NO by H₂ on the Stepped Pd(211) Surface

Catalytic Hydrogenation of p-Chloronitrobenzene to p-Chloroaniline Mediated by γ-Mo₂N