Identification of formate from methanol oxidation on Cu() with infrared spectroscopy

Mudalige, Kanchana; Trenary, Michael

doi:10.1016/s0039-6028(02)01101-9

Cited by 26 publications

(24 citation statements)

References 27 publications

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“…Thus it is highly probable that methoxy is the dominant species on the CM catalyst as well. Methoxy typically adsorbs in an on-top mode on copper single crystal surfaces, [36][37][38] but might be found in a bridged form on the supposedly important step sites as suggested by DFT. 6 Methanol formation from CO 2 /H 2 Fig.…”

Section: Resultsmentioning

confidence: 98%

Different routes to methanol: inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts

Kandemir

Friedrich

Parker

et al. 2016

Phys. Chem. Chem. Phys.

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We have investigated methanol synthesis with model supported copper catalysts, Cu/ZnO and Cu/MgO, using CO/H2 and CO2/H2 as feedstocks. Under CO/H2 both catalysts show chemisorbed methoxy as a stable intermediate, the Cu/MgO catalyst also shows hydroxyls on the support. Under CO2/H2 the catalysts behave differently, in that formate is also seen on the catalyst. For the Cu/ZnO catalyst hydroxyls are present on the metal whereas for the Cu/MgO hydroxyls are found on the support. These results are consistent with a recently published model for methanol synthesis and highlight the key role of ZnO in the process.

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Section: Resultsmentioning

confidence: 98%

Different routes to methanol: inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts

Kandemir

Friedrich

Parker

et al. 2016

Phys. Chem. Chem. Phys.

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“…The chemical species observed in this study are identified by comparing the acquired fragment with those tabulated in the literature. [4,6,13,36] The broad CH 3 OH peak (mass 31 and mass 32) occurs at 340 K. The missing peak of mass 33 indicates the methanol (CH 3 OD) is desorbed as CH 3 OH instead of CH 3 OD. The formaldehyde peak (mass 29 and mass 30) at 350 K is much higher than the CH 3 OH peak.…”

Section: Resultsmentioning

confidence: 99%

“…The adsorption of methanol on metal surfaces has been widely studied as a model system in both fundamental surface science and industry due to a number of relevant heterogeneous catalytic reactions such as hydrogenation of CO to methanol and syntheses of formaldehyde. [1][2][3][4][5] The methoxy fragment is always produced following methanol adsorption as a stable and abundant species at room temperature and it has been proved to be an important intermediate during industrial methanol and formaldehyde production with well-documented use of metal and metal oxide catalysts. [2,6] The generation of methoxy group requires copper atoms to induce metal activated O-H bond scission on the adsorbed methanol atom.…”

Section: Introductionmentioning

confidence: 99%

“…[2,[6][7][8][9] However, in some conditions the formate group is identified on copper surface as a less abundant but more stable intermediate following methanol adsorption. [4,10] A variety of surface science techniques have been performed to detect methanol adsorption on the copper surface, such as Electron Energy Loss Spectroscopy (EELS), Low Energy Electron Diffraction (LEED), Auger Electron Spectroscopy(AES), X-ray Photoelectron Spectroscopy (XPS) and Temperature Programmed Desorption (TPD). [6][7][8][11][12][13] While these traditional surface science techniques could only be operated in ultra-high vacuum (UHV) conditions, with a large enough free mean path for the ion or electron to reach the sample or be collected by detectors, many interesting surface phenomena including the adsorption of methanol were uncovered.…”

Section: Introductionmentioning

confidence: 99%

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Roles of oxygen for methanol adsorption on polycrystalline copper surface revealed by sum frequency generation imaging microscopy

et al. 2016

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The adsorption of atmospheric pressure methanol on the polycrystalline copper surface has been studied by a combination of sum frequency generation imaging microscopy (SFGIM) and temperature programmed desorption (TPD). Methoxy species can be generated by exposing the polycrystalline copper surface to methanol vapor at room temperature. SFGIM results demonstrate that oxygen promotes the surface adsorption of methanol and the increase in the amount of methoxy produced on copper surface. SFGIM orientation analysis suggests the methoxy monolayer is oriented closer to the surface normal with introduction of oxygen. Employing the image statistical analysis approach, the heterogeneities and conformation distribution of methoxy monolayers on copper surface with and without oxygen adsorption are compared. These results illustrate SFGIM indeed could provide more insight for understanding the heterogeneous metal/metal oxide surface in the molecular level.

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“…These features are gradually replaced by a mixture of methoxy and monolayer methanol features until at temperatures of above 270 K methoxy prevails, being visible until about 570 K. The assignment of the vibrational bands as given in Fig. 9 is based on data published for adsorbed methanol [20,21] and methoxy [22][23][24].…”

Section: Formation Of a Methoxy Layermentioning

confidence: 99%

Methanol Adsorption on V2O3(0001)

et al. 2011

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Well ordered V 2 O 3 (0001) layers may be grown on Au (111) surfaces. These films are terminated by a layer of vanadyl groups which may be removed by irradiation with electrons, leading to a surface terminated by vanadium atoms. We present a study of methanol adsorption on vanadyl terminated and vanadium terminated surfaces as well as on weakly reduced surfaces with a limited density of vanadyl oxygen vacancies produced by electron irradiation. Different experimental methods and density functional theory are employed. For vanadyl terminated V 2 O 3 (0001) only molecular methanol adsorption was found to occur whereas methanol reacts to form formaldehyde, methane, and water on vanadium terminated and on weakly reduced V 2 O 3 (0001). In both cases a methoxy intermediate was detected on the surface. For weakly reduced surfaces it could be shown that the density of methoxy groups formed after methanol adsorption at low temperature is twice as high as the density of electron induced vanadyl oxygen vacancies on the surface which we attribute to the formation of additional vacancies via the reaction of hydroxy groups to form water which desorbs below room temperature. Density functional theory confirms this picture and identifies a methanol mediated hydrogen transfer path as being responsible for the formation of surface hydroxy groups and water. At higher temperature the methoxy groups react to form methane, formaldehyde, and some more water. The methane formation reaction consumes hydrogen atoms split off from methoxy groups in the course of the formaldehyde production process as well as hydrogen atoms still being on the surface after being produced at low temperature in the course of the methanol ? methoxy ? H reaction.

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Identification of formate from methanol oxidation on Cu() with infrared spectroscopy

Cited by 26 publications

References 27 publications

Different routes to methanol: inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts

Different routes to methanol: inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts

Roles of oxygen for methanol adsorption on polycrystalline copper surface revealed by sum frequency generation imaging microscopy

Methanol Adsorption on V2O3(0001)

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