Observation of novel intermediates from CH3SH decomposition on Pt(111) with HREELS and NEXAFS

Koestner, R.J.; Stöhr, J.; Gland, John L.; Kollin, E. B.; Sette, F.

doi:10.1016/0009-2614(85)87059-7

Cited by 70 publications

(51 citation statements)

References 29 publications

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“…In this paper we present the results of detailed calculations of the vibrational spectra of methane-thiol and methanethiolate, in the gas phase and adsorbed at high coverage on the (111) surfaces of Ni, Pd, and Pt. Experimental results from HREELS measurements are available for Ni [8,9] and Pt [10,11] substrates, but we do not know of any previous theoretical investigations. For isolated molecular species the calculation of vibrational frequencies and intensities, based on force constants determined analytically from second derivatives of the total energies [12], is now a standard task implemented in many program packages for density-functional calculations such as GAUSSIAN [13] or VASP [14,15].…”

Section: Introductionmentioning

confidence: 99%

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy

Karhánek

Bučko²,

Häfner³

2010

J. Phys.: Condens. Matter

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The vibrational eigenstates of methane-thiol (CH(3)SH) and methane-thiolate (CH(3)S) in the gas phase and in dense monolayers adsorbed on the (111) surfaces of the Ni-group metals have been investigated within the framework of density-functional theory using generalized response and force-constant techniques. For isolated CH(3)SH good agreement of eigenfrequencies and intensities with the measured infrared spectra is achieved. For the CH(3)S radical, experimental information from laser-induced fluorescence spectroscopy is available only for selected eigenmodes. The theoretical predictions show reasonable agreement for the C-H deformation and C-S stretching modes, but predict much higher C-H stretching frequencies in better agreement with estimates based on the vibrational fine structure of the photoemission spectra. For methane-thiol monolayers on Ni(111) and Pt(111) the calculations predict stronger red-shifts of the S-H and C-S stretching modes than reported from high-resolution electron energy loss spectroscopy (HREELS) on condensed multilayers which average over the first layer adsorbed on the metal and further physisorbed molecular layers. For methane-thiolate monolayers the calculations predict modest blue-shifts of the C-H stretching and rocking modes and for the asymmetric C-H deformation modes. Red-shifts are predicted for the symmetric C-H deformation and for the C-S stretching modes. Reasonable agreement with HREELS is achieved. The increased differences between symmetric and asymmetric C-H stretching and deformation modes induced by the adsorption is a consequence of the strongly tilted adsorption geometries.

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Section: Introductionmentioning

confidence: 99%

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy

Karhánek

Bučko²,

Häfner³

2010

J. Phys.: Condens. Matter

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“…Relatively sizable adsorption energies for molecular adsorption of CH 3 SH over the Fe(100) surface indicate that that latter could be used as an in ingredient in affordable sensing instruments for mercaptans compounds. Several studies in the literature have explored adsorption of methanethiol over many surfaces including Fe(100), Pt(111), Ni(110), W(211), Cu(100), Au(111), Cu(111), and Ni(100) . In general, CH 3 SH adsorbs through the sulfur atom with the methyl group pointing outward from the surface.…”

Section: Results and Discutionmentioning

confidence: 99%

“…Both species were found to be stable at all considered coverages up to 150 K. At low coverage and upon heating, these two species are completely decomposed into atomic C and S, and gaseous H 2 , while at high coverages atomic S and gaseous CH 4 are produced . Likewise, a temperature‐induced decomposition of CH 3 SH on the Pt(111) surface produced two other surface intermediates, namely, thiomethoxy (SCH 3 ) and thioformaldehyde (SCH 2 ) …”

Section: Introductionmentioning

confidence: 99%

“…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%

“…13,14 Likewise, a temperature-induced decomposition of CH 3 SH on the Pt(111) surface produced two other surface intermediates, namely, thiomethoxy (SCH 3 ) and thioformaldehyde (SCH 2 ). 9 On the theoretical side, molecular simulation via density functional theory (DFT) calculations provided atomic-basis insight into the interaction of a wide array of molecules with metallic and mineral surfaces. 15,16 To this end, this contribution reports a density functional theory (DFT) study on the modes of interactions between the CH 3 SH molecule over the clean Fe(100) surface.…”

mentioning

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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Electron spectroscopic investigation of ethylmethylsulfide/nickel interface

Syed

Sardar

Yagi

et al. 2003

Surface & Interface Analysis

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To demonstrate the interaction of ethylmethylsulfide (C 2 H 5 SCH 3 ) with an Ni(110) surface, we use xray photoelectron spectroscopy and x-ray absorption near-edge structure measurements to identify the adsorbed sulfur species and their orientation on the surface at low temperature. The S-C 2 H 5 and S-CH 3 bonds are found to be oriented at angles of 46 ± 5• and 14 ± 5• from the surface, respectively. A qualitative estimation of charge transfer from substrate to molecule is carried out by S 1s XPS measurements.

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Observation of novel intermediates from CH3SH decomposition on Pt(111) with HREELS and NEXAFS

Cited by 70 publications

References 29 publications

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy

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

Electron spectroscopic investigation of ethylmethylsulfide/nickel interface

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Observation of novel intermediates from CH3SH decomposition on Pt(111) with HREELS and NEXAFS

Cited by 70 publications

References 29 publications

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy

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

Electron spectroscopic investigation of ethylmethylsulfide/nickel interface

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