Kinetic and mechanistic investigations of the direct synthesis of dimethyl carbonate from carbon dioxide over ceria nanorod catalysts

Marin, Chris M.; Li, Lei; Bhalkikar, Anuja; Doyle, James E.; Zeng, Xiao Cheng; Cheung, Chin Li

doi:10.1016/j.jcat.2016.06.003

Cited by 57 publications

(58 citation statements)

References 23 publications

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“…reaction mechanism of the direct synthesis of dimethyl carbonate from carbon dioxide and methanol, Figure 7. Specifically, a Langmuir-Hinshelwood mechanism that includes carbon dioxide and methanol binding to the catalyst in separate steps, as it was suggested in kinetics studies of the liquid phase DMC formation [30], is consistent with the experimental results. The large K 5 value suggests the irreversibility of the surface reaction.…”

Section: Kinetic Modelingsupporting

confidence: 86%

“…Kinetic studies of the liquid phase synthesis of DMC from methanol and carbon dioxide over CeO 2 [29] and CeO 2 nanorod catalysts [30] have been reported. A reaction rate based on the Langmuir-Hinshelwood mechanism was proposed, including the following steps: adsorption of methanol and carbon dioxide over CeO 2 sites, reaction between adsorbed species (MeOH* + CO 2 *) and desorption of the products (DMC and H 2 O); the surface reaction is the limiting step [29], [30]. The activation energy of the reaction reported was 106 kJ mol −1 [29] and 65 kJ mol −1 [30].…”

Section: Introductionmentioning

confidence: 99%

“…A reaction rate based on the Langmuir-Hinshelwood mechanism was proposed, including the following steps: adsorption of methanol and carbon dioxide over CeO 2 sites, reaction between adsorbed species (MeOH* + CO 2 *) and desorption of the products (DMC and H 2 O); the surface reaction is the limiting step [29], [30]. The activation energy of the reaction reported was 106 kJ mol −1 [29] and 65 kJ mol −1 [30]. However, kinetic results, which are essential to develop a kinetic model that would allow evaluating novel integrated processes to overcome the low equilibrium conversion, are very scarce.…”

Section: Introductionmentioning

confidence: 99%

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Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

Arbeláez-Pérez

Domínguez-Cardozo

Orrego-Romero

et al. 2019

redin

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The catalytic activity for dimethyl carbonate formation from carbon dioxide and methanol over mono and bimetallic Cu:Ni supported on activated carbon is presented. Bimetallic catalysts exhibit higher catalytic activity than the monometallic samples, being Cu:Ni-2:1 (molar ratio) the best catalyst; X-Ray diffraction, transmission electron microscopy, and metal dispersion analysis provided insight into the improved activity. In situ FT-IR experiments were conducted to investigate the mechanism of formation of dimethyl carbonate from methanol and carbon dioxide over Cu-Ni:2-1. The kinetics of the direct synthesis of dimethyl carbonate in gas phase over Cu:Ni-2:1 supported on activated carbon catalyst was experimentally investigated at 12 bar and temperatures between 90 oC and 130 oC, varying the partial pressures of CO2 and methanol. Experimental kinetic data were consistent with a Langmuir–Hinshelwood model that included carbon dioxide and methanol adsorption on catalyst actives sites (Cu, Ni and Cu-Ni), and the reaction of adsorbed CO2 with methoxi species as the rate determining step. The estimated apparent activation energy was 94.2 kJ mol-1.

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Section: Kinetic Modelingsupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

Arbeláez-Pérez

Domínguez-Cardozo

Orrego-Romero

et al. 2019

redin

View full text Add to dashboard Cite

show abstract

“…There is a positive liner relationship of these parameters, suggesting the initial rates of this reaction influenced by the activation of both CO 2 and methanol. This result corresponds to the deduction of Langmuir-Hinshelwood mechanism [37,38]. …”

Section: Kinetic Analysissupporting

confidence: 83%

Surface Reduced CeO2 Nanowires for Direct Conversion of CO2 and Methanol to Dimethyl Carbonate: Catalytic Performance and Role of Oxygen Vacancy

et al. 2018

Catalysts

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Ultralong 1D CeO 2 nanowires were synthesized via an advanced solvothermal method, surface reduced under H 2 atmosphere, and first applied in direct synthesis of dimethyl carbonate (DMC) from CO 2 and CH 3 OH. The micro morphologies, physical parameters of nanowires were fully investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), N 2 adsorption, X-ray photoelectron spectrum (XPS), and temperature-programmed desorption of ammonia/carbon dioxide (NH 3 -TPD/CO 2 -TPD). The effects of surface oxygen vacancy and acidic/alkaline sites on the catalytic activity was explored. After reduction, the acidic/alkaline sites of CeO 2 nanowires can be dramatically improved and evidently raised the catalytic performance. CeO 2 nanowires reduced at 500 • C (CeO 2 _NW_500) exhibited notably superior activity with DMC yield of 16.85 mmol gcat −1 . Furthermore, kinetic insights of initial rate were carried out and the apparent activation energy barrier of CeO 2 _NW_500 catalyst was found to be 41.9 kJ/mol, much tiny than that of CeO 2 _NW catalyst (74.7 KJ/mol).

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“…62 Table 4 compares the equilibrium, kinetic and thermodynamic parameters as obtained in the present study with those reported in the literature. [63][64][65][66][67][68] It seems that a direct comparison of these parameters for different catalysts is not possible as these were prepared using different methods and evaluated under different operating conditions.…”

Section: Chemical Equilibrium Modelingmentioning

confidence: 99%

Dimethyl carbonate synthesis from carbon dioxide using ceria–zirconia catalysts prepared using a templating method: characterization, parametric optimization and chemical equilibrium modeling

et al. 2016

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Kinetic and mechanistic investigations of the direct synthesis of dimethyl carbonate from carbon dioxide over ceria nanorod catalysts

Cited by 57 publications

References 23 publications

Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

Surface Reduced CeO2 Nanowires for Direct Conversion of CO2 and Methanol to Dimethyl Carbonate: Catalytic Performance and Role of Oxygen Vacancy

Dimethyl carbonate synthesis from carbon dioxide using ceria–zirconia catalysts prepared using a templating method: characterization, parametric optimization and chemical equilibrium modeling

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