Methanol dehydrogenation to methyl formate catalyzed by SiO2-, hydroxyapatite-, and MgO-supported copper catalysts and reaction kinetics

Lü, Zhipeng; Gao, Dingsan; Yin, Hengbo; Wang, Aili; Liu, Shuxin

doi:10.1016/j.jiec.2015.07.002

Cited by 52 publications

(29 citation statements)

References 19 publications

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“…The small-sized metallic Cu 0 crystallites also catalyzed the formation of methyl formate via the intermolecular dehydrogenation reaction of methanol. 21 2CH 3 OH = CH 3 OOCH + 2H 2 …”

Section: Resultsmentioning

confidence: 99%

Direct reaction between silicon and methanol over Cu-based catalysts: investigation of active species and regeneration of CuCl catalyst

et al. 2018

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“…The small-sized metallic Cu 0 crystallites also catalyzed the formation of methyl formate via the intermolecular dehydrogenation reaction of methanol. 21 2CH 3 OH = CH 3 OOCH + 2H 2 …”

Section: Resultsmentioning

confidence: 99%

Direct reaction between silicon and methanol over Cu-based catalysts: investigation of active species and regeneration of CuCl catalyst

et al. 2018

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“…The ratio of the selectivity of MF to CH 2 O reported by Kaichev and co-workers ranges from 16 to 28 with CH 3 OH conversion rates ranging from 45% to 85%, 31 so our estimate based on the cluster model calculations is in reasonable agreement with their results, although our simple model does not allow us to estimate the effect of the CH 3 OH conversion rate on the product selectivity. With the slab model, the energy barrier was calculated to be 1.19 eV for step [2] and 1.01 eV for step [11], which has a larger difference of 0.18 eV. However, step [10] was predicted to have a higher energy barrier of 1.16 eV than step [11], so our simple model may not work properly.…”

Section: The Journal Of Physical Chemistry Cmentioning

confidence: 93%

“…With the slab model, the energy barrier was calculated to be 1.19 eV for step [2] and 1.01 eV for step [11], which has a larger difference of 0.18 eV. However, step [10] was predicted to have a higher energy barrier of 1.16 eV than step [11], so our simple model may not work properly. Nevertheless, even with the slab model, the energy barrier for the ODH of CH 3 OCH 2 O* was predicted to be lower than that of CH 3 O*, which should be the primary reason for the preferred formation of MF in CH 3 OH oxidation.…”

Section: The Journal Of Physical Chemistry Cmentioning

confidence: 93%

“…Due to the poor efficiency of the above process, ,− there is significant interest in developing greener catalytic processes for MF synthesis. During the past decade, a number of different routes have been explored, and MF can be synthesized at varying efficiency by CH 3 OH dehydrogenation, − CH 3 OH oxidation, ,,,,− dimethyl ether (CH 3 OCH 3 , DME) oxidation, CO 2 hydrogenation or reduction in CH 3 OH, ,− CH 3 OH carbonylation, , as well as directly from synthesis gas. − …”

Section: Introductionmentioning

confidence: 99%

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Catalytic Mechanisms of Methanol Oxidation to Methyl Formate on Vanadia–Titania and Vanadia–Titania–Sulfate Catalysts

Wang

Ren

et al. 2016

J. Phys. Chem. C

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Density functional theory calculations were carried out using both cluster and slab models to investigate the catalytic reaction network and the effect of sulfate promoter on methanol selective oxidation using the V2O5/TiO2 catalyst. The hemiacetal mechanism was reaffirmed to be the most favorable reaction pathway for the formation of methyl formate (MF) by the prediction of another reaction pathway involving formic acid. Molecular oxygen was found to assist the desorption of the reaction products from the reduced catalyst active site, both formaldehyde and methyl formate (MF). The mechanism of catalyst regeneration was elucidated based solely on first-principles calculations, which involve the conversion of another methanol molecule to formaldehyde over a peroxo species. This leads to our formulation of a complete catalytic reaction network for methanol selective oxidation to formaldehyde and MF on the V2O5/TiO2 catalyst. In addition, the detailed mechanism for the formation of formaldehyde and MF was also predicted on the sulfate-promoted V2O5/TiO2 catalyst. Based on the calculated reaction networks, the preferred formation of MF on the V2O5/TiO2-based catalysts was attributed to the lower energy barrier of the oxidative dehydrogenation (ODH) of the CH3OCH2O* intermediate than that of CH3O*. Furthermore, our calculated energy barriers also suggest that the sulfate-promoted V2O5/TiO2 catalyst has not only higher catalytic activity for methanol conversion but also higher selectivity of MF over CH2O, consistent with previous experimental observations. The sulfate promoter was found to increase the positive charge at the V site, leading to a lower energy barrier for the ODH of CH3O* than the unpromoted catalyst.

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“…Au containing catalysts had higher total basicity than the corresponding Pt catalysts. The basicity of the catalysts was at a low level based on the CO 2 -TPD [ 29 ], which should be advantageous for the desorption of formed CO 2 from the catalyst surface during DCM oxidation. The basic sites can be assigned low, medium, and high according to different CO 2 desorption ranges at 80–140 °C, 160–240 °C, and >300 °C, respectively [ 30 ].…”

Section: Resultsmentioning

confidence: 99%

Oxidation of Dichloromethane over Au, Pt, and Pt-Au Containing Catalysts Supported on γ-Al2O3 and CeO2-Al2O3

2020

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Au, Pt, and Pt-Au catalysts supported on Al2O3 and CeO2-Al2O3 were studied in the oxidation of dichloromethane (DCM, CH2Cl2). High DCM oxidation activities and HCl selectivities were seen with all the catalysts. With the addition of Au, remarkably lower light-off temperatures were observed as they were reduced by 70 and 85 degrees with the Al2O3-supported and by 35 and 40 degrees with the CeO2-Al2O3-supported catalysts. Excellent HCl selectivities close to 100% were achieved with the Au/Al2O3 and Pt-Au/Al2O3 catalysts. The addition of ceria on alumina decreased the total acidity of these catalysts, resulting in lower performance. The 100-h stability test showed that the Pt-Au/Al2O3 catalyst was active and durable, but the selectivity towards the total oxidation products needs improvement. The results suggest that, with the Au-containing Al2O3-supported catalysts, DCM decomposition mainly occurs via direct DCM hydrolysis into formaldehyde and HCl followed by the oxidation of formaldehyde into CO and CO2.

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Methanol dehydrogenation to methyl formate catalyzed by SiO2-, hydroxyapatite-, and MgO-supported copper catalysts and reaction kinetics

Cited by 52 publications

References 19 publications

Direct reaction between silicon and methanol over Cu-based catalysts: investigation of active species and regeneration of CuCl catalyst

Direct reaction between silicon and methanol over Cu-based catalysts: investigation of active species and regeneration of CuCl catalyst

Catalytic Mechanisms of Methanol Oxidation to Methyl Formate on Vanadia–Titania and Vanadia–Titania–Sulfate Catalysts

Oxidation of Dichloromethane over Au, Pt, and Pt-Au Containing Catalysts Supported on γ-Al2O3 and CeO2-Al2O3

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