Adsorption of nitrobenzene, aniline and nitroanilines on the surface of a basal face of graphite

Yashkina, E. A.; Svetlov, D. A.; Yashkin, S. N.

doi:10.1134/s0036024412110295

Cited by 7 publications

(4 citation statements)

References 19 publications

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“…It is possible that this negative activation energy (absolute value) is related to the heat of adsorption of aniline monomer vapor on the substrate surface. 52 However, our value is lower than the heat of adsorption values of aniline vapor reported in the literature, for example, 42−50 kJ/mol based on adsorption experiments on graphitized carbon black materials, 53,54 and 66−69 kJ/mol based on Monte Carlo simulations and quantum chemical calculations on an ice surface. 55 The disparity could be rationalized by recognizing that our value is most likely not simply because of the heat of adsorption but an effective activation energy that accounts for both adsorption and surface reaction.…”

Section: ■ Results and Discussioncontrasting

confidence: 69%

Deposition Behavior of Polyaniline on Carbon Nanofibers by Oxidative Chemical Vapor Deposition

Rafie

Kalra

et al. 2020

Langmuir

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Oxidative chemical vapor deposition (oCVD) offers unique advantages as a liquid-free processing technique in synthesizing and integrating conducting polymers, including polyaniline (PANI), by enabling conformal coatings onto nanostructured substrates, like carbon nanofibers. With relatively thick nanofiber mats, the challenge is to ensure uniform coating thickness through the porous substrates. Here, the substrate temperature during oCVD is found to be a primary factor influencing PANI coating uniformity. Coating uniformity is enhanced by operating at a higher substrate temperature, where monomer adsorption is believed to be limiting relative to intrinsic reaction kinetics. Also, a higher substrate temperature leads to significantly less PANI oligomers and more PANI in the emeraldine oxidation state. A systematic study of oCVD kinetics with substrate temperature shows a reaction-limited regime at lower substrate temperatures with an activation energy of 12.0 kJ/ mol, which is believed to be controlled by the self-catalyzed PANI polymerization reaction that transitions at higher substrate temperatures above 90 °C to an adsorption-limited regime as indicated by a negative activation energy of −18.8 kJ/mol. Overall, by operating within an adsorption-limited oCVD regime, more uniform oCVD PANI coatings on electrospun carbon nanofiber mats have been achieved.

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Section: ■ Results and Discussioncontrasting

confidence: 69%

Deposition Behavior of Polyaniline on Carbon Nanofibers by Oxidative Chemical Vapor Deposition

Rafie

Kalra

et al. 2020

Langmuir

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“…This causes the experimentally measured binding energies of polar substances adsorbed on this material to be systematically lower by ∼1–2 kcal/mol compared with the data obtained using Sterling MT. In particular, the adsorption enthalpy of nitrobenzene adsorbed on Carbopack C HT is reported to be −11.7 kcal/mol . This number corresponds well with the binding energy calculated in a previous study by our group at the BLYP-D2(PBC) level (−11.6 kcal/mol) (RT value is included, see Table ) .…”

Section: Resultssupporting

confidence: 87%

“…In particular, the adsorption enthalpy of nitrobenzene adsorbed on Carbopack C HT is reported to be −11.7 kcal/mol. 59 This number corresponds well with the binding energy calculated in a previous study by our group at the BLYP-D2(PBC) level (−11.6 kcal/mol) (RT value is included, see Table 1). 13 To obtain direct conformation of this statement the experimental measurement of the adsorption energy for pyridine interacting with Carbopack C HT instead of with Sterling MT has been performed under the same experimental conditions as in ref 27.…”

Section: Adsorption Energies and Enthalpiessupporting

confidence: 82%

“…In particular, all experimental data listed in Table 1 were obtained on graphitized thermal carbon black Sterling MT. However, in the experimental publication 59 it is clearly stated that the best representation of an ideal graphite phase (the model considered in this study) contains different graphitized thermal carbon blackCarbopack C HT. This causes the experimentally measured binding energies of polar substances adsorbed on this material to be systematically lower by ∼1−2 kcal/mol compared with the data obtained using Sterling MT.…”

Section: Adsorption Energies and Enthalpiesmentioning

confidence: 99%

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Toward Accurate and Efficient Predictions of Entropy and Gibbs Free Energy of Adsorption of High Nitrogen Compounds on Carbonaceous Materials

Scott

Gorb²,

Burns³

et al. 2014

J. Phys. Chem. C

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The adsorption of high nitrogen compounds (HNCs) on the selected adsorption sites of carbonaceous materials from the gas phase has been investigated by ab initio quantum chemical methods at the density functional level applying both periodic and cluster approaches with M06-2X and BLYP functionals including dispersion forces (BLYP-D2). Among the possible structures of the adsorption complexes, the most stable systems possess nitrogen-containing heterocycles in a parallel orientation toward the modeled carbon surface. The adsorption enthalpies, calculated using the rigid rotor-harmonic oscillator approach (RRHO), were in good agreement with available experimental data. This approach was shown to provide sufficiently accurate adsorption enthalpies from the gas phase for the HNC−carbon systems. The vibrational, rotational, and translation contributions to the adsorption entropy were also analyzed by the approach extended beyond the RRHO scheme. The effects of anharmonic vibrations and internal rotations of the adsorbate on the adsorption sites of the modeled carbon surface were estimated. The Gibbs free energies calculated using the RRHO approach were adjusted to take into account the heterogeneity of the carbon surfaces and underestimation of the adsorption enthalpies at the BLYP-D2(PBC) level. The corrected Gibbs free energy values of adsorption are negative for all of the investigated HNC−carbon systems, and they agree well with available experimental data. This suggests an effective adsorption of selected high nitrogen compounds on carbonaceous materials from the gas phase at 298.15 K. Partition coefficients for distribution of high nitrogen compounds on modeled carbon surfaces were also predicted in good agreement with the experimental results.

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Thermodynamic characteristics of the adsorption of benzene derivatives from water—organic eluents on porous graphite-like adsorbent under conditions of equilibrium HPLC

et al. 2020

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Adsorption of nitrobenzene, aniline and nitroanilines on the surface of a basal face of graphite

Cited by 7 publications

References 19 publications

Deposition Behavior of Polyaniline on Carbon Nanofibers by Oxidative Chemical Vapor Deposition

Deposition Behavior of Polyaniline on Carbon Nanofibers by Oxidative Chemical Vapor Deposition

Toward Accurate and Efficient Predictions of Entropy and Gibbs Free Energy of Adsorption of High Nitrogen Compounds on Carbonaceous Materials

Thermodynamic characteristics of the adsorption of benzene derivatives from water—organic eluents on porous graphite-like adsorbent under conditions of equilibrium HPLC

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