Dehydrogenation of methanol to methyl formate over copper catalysts

Tonner, Stephen P.; Trimm, D.L.; Wainwright, Mark; Cant, Noel W.

doi:10.1021/i300015a012

Cited by 101 publications

(41 citation statements)

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“…In line with our results, acetaldehyde and methanol were previously obtained as main products over Cu-AC catalysts [17]. In the case of catalyst 50% Cu-AC, the high Cu particle size favored the production of methyl formate by dehydrogenation of methanol Reaction (7), as previously reported [33]. Figure 4a,b summarize the effect of the applied current and the reaction temperature on the steady state CO 2 consumption rate (after 350 min of polarization), respectively.…”

Section: Co 2 Conversion Electrocatalytic Experimentssupporting

confidence: 92%

Low-Temperature Electrocatalytic Conversion of CO2 to Liquid Fuels: Effect of the Cu Particle Size

et al. 2018

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A novel gas-phase electrocatalytic system based on a low-temperature proton exchange membrane (Sterion) was developed for the gas-phase electrocatalytic conversion of CO 2 to liquid fuels. This system achieved gas-phase electrocatalytic reduction of CO 2 at low temperatures (below 90 • C) over a Cu cathode by using water electrolysis-derived protons generated in-situ on an IrO 2 anode. Three Cu-based cathodes with varying metal particle sizes were prepared by supporting this metal on an activated carbon at three loadings (50, 20, and 10 wt %; 50% Cu-AC, 20% Cu-AC, and 10% Cu-AC, respectively). The cathodes were characterized by N 2 adsorption-desorption, temperature-programmed reduction (TPR), and X-ray diffraction (XRD) and their performance towards the electrocatalytic conversion of CO 2 was subsequently studied. The membrane electrode assembly (MEA) containing the cathode with the largest Cu particle size (50% Cu-AC, 40 nm) showed the highest CO 2 electrocatalytic activity per mole of Cu, with methyl formate being the main product. This higher electrocatalytic activity was attributed to the lower Cu-CO bonding strength over large Cu particles. Different product distributions were obtained over 20% Cu-AC and 10% Cu-AC, with acetaldehyde and methanol being the main reaction products, respectively. The CO 2 consumption rate increased with the applied current and reaction temperature.

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Section: Co 2 Conversion Electrocatalytic Experimentssupporting

confidence: 92%

Low-Temperature Electrocatalytic Conversion of CO2 to Liquid Fuels: Effect of the Cu Particle Size

et al. 2018

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“…A series of thermal catalytic investigations on gas-phase dehydrogenation of CH 3 OH to HCOOCH 3 over copper-based catalysts 31 3 OH were coadsorbed, we found that the cross-coupling reaction occurs (see Figure 5), and in a separate experiment that started with adsorbed CH 2 O, we saw no evidence for formation of HCOOCH 3 , indicating that the self-coupling reaction does not occur ( Figure 6). Thus, we conclude that the cross-coupling reaction also proceeds An experiment with coadsorbed CH 3 O and CH 2 O was performed to verify that the cross-coupling reaction was photocatalyzed and occurred during irradiation, rather than during TPD via a thermal mechanism.…”

Section: Results and Analysismentioning

confidence: 95%

Methyl Formate Production on TiO₂(110), Initiated by Methanol Photocatalysis at 400 nm

et al. 2013

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Previous observations of methyl formate (HCOOCH 3 ) during the photo-oxidation of methanol (CH 3 OH) on TiO 2 catalysts suggested that photocatalysis on TiO 2 could be used to build up complex molecules from a single precursor. We have investigated the mechanism of HCOOCH 3 formation by irradiating a CH 3 OH-adsorbed TiO 2 (110) surface with 400 nm light at low surface temperatures. Through the detection of volatile products after irradiation by temperature programmed desorption, we have found, as previously reported [Phillips et al. J. Am. Chem. Soc. 2013, 135, 574−577] that HCOOCH 3 is formed by the cross-coupling reaction of CH 3 O and CH 2 O, which are products of the first and second dissociation steps, respectively, in the stepwise photocatalysis of CH 3 OH on TiO 2 (110). Unlike the previous study, we have observed the photocatalytic production of HCOOCH 3 without preoxidation of the surface, and we have concluded that the final reaction step to produce HCOOCH 3 (i.e., the cross-coupling reaction of CH 2 O with CH 3 O) does not involve a transient HCO intermediate.

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“…In the reaction, methanol was converted to methyl formate, CO, and H 2 . Although formaldehyde was supposed to be firstly produced, it was not detected in the [20] suggested that the formation of methyl formate from formaldehyde was rapid and the formation of formaldehyde from methanol was the rate-controlling step, which well explained the absence of formaldehyde in the products. For the Cu(5)/SiO 2 , Cu(10)/SiO 2 , and Cu(20)/SiO 2 catalysts, with increasing reaction temperatures from 200 to 280 8C,the conversions of methanol increased from 0.9% to 50.1%, 2.3% to 55.5%, and 4.8% to 59.2%, respectively (Fig.…”

Section: Catalytic Activities Of Copper-based Catalysts In Methanol Dmentioning

confidence: 99%

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

Lü

Gao

Yin

et al. 2015

Journal of Industrial and Engineering Chemistry

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Dehydrogenation of methanol to methyl formate over copper catalysts

Cited by 101 publications

References 2 publications

Low-Temperature Electrocatalytic Conversion of CO2 to Liquid Fuels: Effect of the Cu Particle Size

Low-Temperature Electrocatalytic Conversion of CO2 to Liquid Fuels: Effect of the Cu Particle Size

Methyl Formate Production on TiO₂(110), Initiated by Methanol Photocatalysis at 400 nm

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

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Dehydrogenation of methanol to methyl formate over copper catalysts

Cited by 101 publications

References 2 publications

Low-Temperature Electrocatalytic Conversion of CO2 to Liquid Fuels: Effect of the Cu Particle Size

Low-Temperature Electrocatalytic Conversion of CO2 to Liquid Fuels: Effect of the Cu Particle Size

Methyl Formate Production on TiO2(110), Initiated by Methanol Photocatalysis at 400 nm

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

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Methyl Formate Production on TiO₂(110), Initiated by Methanol Photocatalysis at 400 nm