The mechanism of methanol decomposition on Fe(100): Comparison to methanethiol decomposition

Albert, M.R.; Lu, Jiong Ping; Bernasek, Steven L.; Dwyer, Daniel J.

doi:10.1016/0039-6028(89)90575-x

Cited by 34 publications

(16 citation statements)

References 41 publications

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“…CH 3 OH and HCOOH are organic molecules suggested to be common prebiotic species , and contain an −OH group, which is the typical functional group that is phosphorylated in biochemical systems. Most of the experiments for CH 3 OH adsorption on iron- and nickel-containing substrates suggest that CH 3 OH dissociates into methoxy (CH 3 O−) at a wide range of surface temperatures, − , although there are few examples of molecular nondissociative adsorption . In some cases the dissociation of methanol was linked to defect sites on the surface .…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Water, Methanol, and Formic Acid on Fe₂NiP, a Meteoritic Mineral Analogue

et al. 2017

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The surface of an analogue to the meteoritic mineral schreibersite or (Fe,Ni) 3 P was investigated to provide insight into the interaction of the mineral surface with prebiotic molecules such as water, methanol, and formic acid. A protocol for creating synthetic metal-phosphide samples with a surface reflectivity suitable for reflection−absorption infrared spectroscopy (RAIRS) was developed and is outlined in this paper. Scanning electron microscopy coupled with energy dispersive spectroscopy revealed an average defect size less than 1 μm and evidence of subsurface phosphorus segregation. At surface temperatures between 120 and 140 K, RAIRS spectra indicate that water and formic acid interact molecularly with surface atoms, while methanol appears to dissociate into methoxy and protons upon adsorption. The observed infrared spectra provide insight into the adsorption geometries of these prebiotic molecules on synthetic schreibersite. This data suggests the importance of the schreibersite mineral surface in aqueous-phase schreibersite-mediated phosphorylation experiments that have been performed by others and strengthens the argument that schreibersite-induced chemistry could occur in astrochemical environments.

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Section: Introductionmentioning

confidence: 99%

Adsorption of Water, Methanol, and Formic Acid on Fe₂NiP, a Meteoritic Mineral Analogue

et al. 2017

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“…The HREElS and XPS data for adsorption of CH 3 SH indicate that surface thiomethoxy (─SCH 3 ) and surface methyl (─CH 3 ) were both detected as intermediates in the thermal decomposition of methanethiol above the Fe(100) surface. 4 Experimental profiles of products also indicated the formation of CH 4 molecules. The thiomethoxy (─SCH 3 ) was shown to be stable at low temperature and upon heating to higher temperatures.…”

Section: Dissociation Into ─Ch 3 and ─Shmentioning

confidence: 95%

“…The sulfur loads in petroleum fuels branch into various compounds, most notably, thiols, disulfides, sulfides, and thiophenes. 3 Interaction of methanethiol (CH 3 SH) with numerous surfaces were thoroughly investigated from many perspectives on different metallic surfaces, Fe(100), 4,5 Cu(111), 6 Cu(100), 7 Pt(111), 8,9 and Ni(100). 10 Generally, the CH 3 SH molecule adsorbs through its sulfur atom, whereas the methyl group points outward from the surface.…”

mentioning

confidence: 99%

“…10 Generally, the CH 3 SH molecule adsorbs through its sulfur atom, whereas the methyl group points outward from the surface. 7,10 Experimentally, adsorption of the methanethiol molecule on metal surfaces was shown to result in the fission of the S─H bond at relatively low temperatures, most notably on the surfaces of Ni(100), 10 Fe(100), 4,5 Cu(100), 7 Ni(111), 11 and Ni(110). 12 Using high-resolution energy electron loss spectroscopy (HREELS), the thiomethoxy (CH 3 S) adduct was identified on Fe(100), Pt(111), Cu(100), and Ni(110) surfaces and by ultraviolet photoelectron spectroscopy (UPS) on the Ni(100) surface.…”

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confidence: 99%

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Adsorption and dissociation of the methanethiol (CH₃SH) molecule on the Fe(100) surface

Saraireh

Altarawneh

Tarawneh

2019

Surface & Interface Analysis

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These contributions explore interaction modes between the methanethoil (CH3SH) molecule and the Fe(100) surface via implementing accurate density functional theory (DFT) calculations with the inclusion of van der Waals corrections. We consider three adsorption sites over the Fe(100) surface, namely, top(T), bridge (B), and hollow (H) sites as potential catalytic active sites for the molecular and dissociative adsorption of the CH3SH molecule. The molecular adsorption structures are found to occupy either B or T sites with former sites holding higher stability by 0.17 eV. The inclusion of van der Waals corrections refound to slightly alter adsorption energies. For instance, adsorption energies increased by ~0.18 and ~0.21 eV for B and T structure, respectively, in reference to values obtained by the plain generalized gradient approximation (GGA) functional. A stability ordering of the dissociation products was found to follow the sequence (CH4, S) > (CH3, S, H) > (─SCH3, H) > (─CH3, SH). The differential charge density distributions were examined to underpin prominent electronic contributing factors. Direct fission of C─S bond in the CH3SH molecule attains exothermic values in the range 2.0 to 2.1 eV. The most energetically favorable sites for the surface‐mediated fission of the thiol's S─H bond correspond to the structure where the ─SCH3 and H are both situated on hollow sites with an adsorption energy of −2.43 eV. Overall, we found that inclusion of van der Waals functional to change the binding energies more noticeably in case of dissociative adsorption structures. The results presented herein should be instrumental in efforts that aim to design stand‐alone Fe desulfurization catalysts.

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“…This conclusion is contrary to that reached by the Exxon group who, in their original study of this system, postulated that these complexes contained methoxy intermediates formed from decomposition of methanol following the initial chemisorption step. 5,7,8 On most transition metal surfaces, including Fe͑110͒ 21 and Fe͑100͒, 22 methanol undergoes dissociative chemisorption at or below room temperature to form a stable methoxy intermediate, which in turn decomposes to form surface-bound CO and H as the surface temperature is increased. In the present experiment, the low temperature at which the iron cluster- methanol reactions take place ͑ϳ80 K͒ combined with the short time scale from reaction to mass spectrometric detection ͑ϳ10 Ϫ3 s͒ would tend to favor the observation of the molecularly bound precursor rather than the ultimate, most stable reaction product͑s͒.…”

Section: A Photodissociation Action Spectramentioning

confidence: 99%

The infrared photodissociation spectra of Fen(CH3OH)m complexes and their deuterated analogs near 10μ

Knickelbein

1996

The Journal of Chemical Physics

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Electronic structures of cobalt cluster cations: Photodissociation spectroscopy of Co+ n Ar (n=3-5) in the visible to nearinfrared range OD͒ m ͑nϭ5-15; mϭ1,2͒ have been recorded from 920-1090 cm Ϫ1 . Analysis of the spectral features indicates that in all cases, molecularly adsorbed methanol is the absorbing chromophore, with no evidence of methoxy formation. The observed frequencies for the C-O stretching vibration and other vibrational modes are shifted ϳ40 cm Ϫ1 to the red of the corresponding fundamentals of gas-phase methanol. The spectral shifts and thus the magnitude of the cluster-methanol interaction are observed to be independent of iron cluster size over the size range studied, implying an insensitivity of the interaction to the underlying cluster structure.

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The mechanism of methanol decomposition on Fe(100): Comparison to methanethiol decomposition

Cited by 34 publications

References 41 publications

Adsorption of Water, Methanol, and Formic Acid on Fe₂NiP, a Meteoritic Mineral Analogue

Adsorption of Water, Methanol, and Formic Acid on Fe₂NiP, a Meteoritic Mineral Analogue

Adsorption and dissociation of the methanethiol (CH₃SH) molecule on the Fe(100) surface

The infrared photodissociation spectra of Fen(CH3OH)m complexes and their deuterated analogs near 10μ

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The mechanism of methanol decomposition on Fe(100): Comparison to methanethiol decomposition

Cited by 34 publications

References 41 publications

Adsorption of Water, Methanol, and Formic Acid on Fe2NiP, a Meteoritic Mineral Analogue

Adsorption of Water, Methanol, and Formic Acid on Fe2NiP, a Meteoritic Mineral Analogue

Adsorption and dissociation of the methanethiol (CH3SH) molecule on the Fe(100) surface

The infrared photodissociation spectra of Fen(CH3OH)m complexes and their deuterated analogs near 10μ

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Adsorption of Water, Methanol, and Formic Acid on Fe₂NiP, a Meteoritic Mineral Analogue

Adsorption of Water, Methanol, and Formic Acid on Fe₂NiP, a Meteoritic Mineral Analogue

Adsorption and dissociation of the methanethiol (CH₃SH) molecule on the Fe(100) surface