RAIRS and TPD Study of Methyl Formate, Ethyl Formate, and Methyl Acetate on Ni(111)

Zahidi, E.; Castonguay, Martin; McBreen, Peter H.

doi:10.1021/ja00092a040

Cited by 53 publications

(83 citation statements)

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“…This is based on the presence of ester, aldehyde, and epoxide functional groups. Methyl acetate and ethyl formate have been shown to exhibit similar desorption behaviour to that of methyl formate when adsorbed on metal surfaces, 33 supporting these predictions, whilst ethylene oxide has previously been classified as an intermediate species by Occhiogrosso et al 55 Since ethylene oxide contains an epoxide functional group, it is probable that this molecule will show an additional desorption feature due to the interaction with water ice and hence we extend the classification of ethylene oxide to a complex intermediate species.…”

Section: Our Complex Intermediate Classification Extends That Of Collsupporting

confidence: 84%

“…The shift in the C= =O band can be assigned to an interaction between the methyl formate molecules and the ASW. A similar red-shift was observed when methyl formate was adsorbed on metallic surfaces 32,33 and is consistent with the additional desorption peak which is observed in the methyl formate TPD spectra on both ASW and CI films, assigned to the desorption of methyl formate bonded directly to water (Figures 1(a) and 1(b)). Following annealing to 110 K ( Figure 2(b)), the pure ice undergoes a structural ordering leading to changes in the infrared spectrum, including band splitting, spectral shifts, and changes in band intensity, as described previously.…”

Section: Rairssupporting

confidence: 83%

“…The nature of the interaction between methyl formate and water can be inferred by comparison with adsorption on metallic surfaces and with DFT calculations on water ice surfaces. RAIRS studies of the adsorption of methyl formate on Ag{111} 32 and Ni{111} 33 have shown that the molecule adopts a structure where the carbonyl group is oriented towards the substrate, forming a strongly physisorbed or weakly chemisorbed structure. DFT calculations for methyl formate adsorption on water ice also show that methyl formate interacts with the surface via the carbonyl group.…”

Section: Tpdmentioning

confidence: 99%

“…31 Similarly, there are a very limited number of studies investigating methyl formate interactions with water ice surfaces, with a majority of the work focusing on thermal processing on metallic surfaces. [32][33][34] Bertin and co-workers presented a study of methyl formate and acetic acid adsorption and desorption from ASW and CI films that combined experiment and theory. 6,35 This study focused on the interaction of submonolayer films with water ices using TPD and RAIRS at 80 K. The only studies at lower temperatures (16 K) have focused on the formation of methyl formate via the ion irradiation of methanol and CO ices.…”

Section: Introductionmentioning

confidence: 99%

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Trapping and desorption of complex organic molecules in water at 20 K

Burke

Puletti

Woods

et al. 2015

The Journal of Chemical Physics

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Laser desorption time-of-flight mass spectrometry of ultraviolet photo-processed ices Rev. Sci. Instrum. 85, 104501 (2014); 10.1063/1.4896754The release of trapped gases from amorphous solid water films. II. "Bottom-up" induced desorption pathways J. Chem. Phys. 138, 104502 (2013) The formation, chemical, and thermal processing of complex organic molecules (COMs) is currently a topic of much interest in interstellar chemistry. The isomers glycolaldehyde, methyl formate, and acetic acid are particularly important because of their role as pre-biotic species. It is becoming increasingly clear that many COMs are formed within interstellar ices which are dominated by water. Hence, the interaction of these species with water ice is crucially important in dictating their behaviour. Here, we present the first detailed comparative study of the adsorption and thermal processing of glycolaldehyde, methyl formate, and acetic acid adsorbed on and in water ices at astrophysically relevant temperatures (20 K). We show that the functional group of the isomer dictates the strength of interaction with water ice, and hence the resulting desorption and trapping behaviour. Furthermore, the strength of this interaction directly affects the crystallization of water, which in turn affects the desorption behaviour. Our detailed coverage and composition dependent data allow us to categorize the desorption behaviour of the three isomers on the basis of the strength of intermolecular and intramolecular interactions, as well as the natural sublimation temperature of the molecule. This categorization is extended to other C, H, and O containing molecules in order to predict and describe the desorption behaviour of COMs from interstellar ices. C 2015 AIP Publishing LLC.[http://dx

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Section: Our Complex Intermediate Classification Extends That Of Collsupporting

confidence: 84%

Section: Rairssupporting

confidence: 83%

Section: Tpdmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Trapping and desorption of complex organic molecules in water at 20 K

Burke

Puletti

Woods

et al. 2015

The Journal of Chemical Physics

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“…The bands at 1465 and 1160 cm -1 could be assigned to the asymmetric bending and rocking of the OCH 3 group ( aOCH3 and  OCH3 ) of gas-phase methyl acetate [61][62][63], respectively.…”

Section: Evidence Of Surface Species Formed During Methanol Carbonylamentioning

confidence: 99%

Methanol carbonylation catalyzed by TiO2–supported gold: An in-situ infrared spectroscopic investigation

Martinez-Ramirez

Flores-Escamilla

Berumen-España

et al. 2015

Applied Catalysis A: General

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Reaction Pathways of Biomass‐Derived Oxygenates over Metals and Carbides: From Model Surfaces to Supported Catalysts

2015

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The conversion of lignocellulosic biomass‐derived oxygenates into renewable fuels and chemicals requires the control of bond‐scission sequences. For example, selective CO/CO bond scission is needed to reduce the oxygen content and thus increase the energy density to produce renewable fuels. On the other hand, the control of CC bond scission is desired for producing H2 and suppressing side products from CO/CO bond‐scission reactions. In this review, recent advances in the utilization of bimetallic and metal carbide catalysts that demonstrate enhanced performance and/or low cost for the selective CC and CO/CO bond‐scission reactions, are summarized. Furthermore, the importance of combining density function theory (DFT) calculations, microkinetic modeling, and ultrahigh vacuum (UHV) experiments on single‐crystal model surfaces with reactor evaluations over the corresponding powder catalysts is illustrated. General trends and future opportunities for the control of bond‐scission sequences of biomass‐derived oxygenates are also discussed.

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RAIRS and TPD Study of Methyl Formate, Ethyl Formate, and Methyl Acetate on Ni(111)

Cited by 53 publications

References 0 publications

Trapping and desorption of complex organic molecules in water at 20 K

Trapping and desorption of complex organic molecules in water at 20 K

Methanol carbonylation catalyzed by TiO2–supported gold: An in-situ infrared spectroscopic investigation

Reaction Pathways of Biomass‐Derived Oxygenates over Metals and Carbides: From Model Surfaces to Supported Catalysts

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